2-amino-4-phenylamino-1,3,5-triazinyl reactive dyestuffs, process for their preparation and their use dye cellulose or polyamides

ABSTRACT

Reactive dyestuffs have the following formula ##STR1## in which D is the radical of an organic dyestuff 
     B is a direct bond or a bridging member on a ring C atom of an aromatic-carbocyclic or on a ring C atom or N atom of an aromatic-heterocyclic ring in D, 
     R a , R b , identical or different, are H, C 1  -C 4  -alkyl or C 1  -C 4  -alkyl substituted by OH, CN, CO 2  H, OSO 3  H or SO 3  H, 
     U is Cl, F or a pyridinium radical which is unsubstituted or substituted by CO 2  H, CONH 2 , SO 3  H or C 1  -C 4  -alkyl, 
     W is straight-chain or branched C 1  -C 6  -alkylene, 
     Y is CH═CH 2  or CH 2  --CH 2  --X, in which 
     X is a radical which can be eliminated by alkali, 
     V is H, halogen, C 1  -C 4  -alkoxy, C 1  -C 3  -alkyl, CN, COOH, CONH 2 , SO 3  H.

This application is a continuation of application Ser. No. 839,457,filed Feb. 20, 1992, now abandoned.

The present invention relates to new water-soluble reactive dyestuffs,processes for their preparation and their use for dyeing.

Dyeing with reactive dyestuffs has recently led to increasing demands onthe quality and economy of the dyeing processes. As a result, there isstill a demand for new reactive dyestuffs which have improved propertieswith respect to fastness properties and processability. EP-A-307 817 andJP-A-72/23708 have already disclosed reactive dyestuffs which are basedon azo dyestuffs and have two reactive groups.

The present invention relates to new reactive dyestuffs of the formula##STR2## in which

D is the radical of an organic dyestuff

B is a direct bond or a bridging member on a ring C atom of anaromatic-carbocyclic or on a ring C atom or N atom of anaromatic-heterocyclic ring in D,

R_(a), R_(b), identical or different, are H, C₁ -C₄ -alkyl or C₁ -C₄-alkyl substituted by OH, CN, CO₂ H, OSO₃ H or SO₃ H,

U is Cl, F or a pyridinium radical which is unsubstituted or substitutedby CO₂ H, CONH₂, SO₃ H or C₁ -C₄ -alkyl,

W is straight-chain or branched C₁ -C₆ -alkylene,

Y is CH═CH₂ or CH₂ --CH₂ --X, in which

X is a radical which can be eliminated by alkali,

V is H, halogen, CC₁ -C₄ -alkoxy, CC₁ -C₃ -alkyl, CN, COOH, CONH₂,

with the proviso that

a) D is the radical of a dyestuff from the formazan, phthalocyanine,anthraquinone and triphendioxazine series if W is --CH₂ --,

b) D is the radical of a dyestuff from the formazan, phthalocyanine,anthraquinone and triphendioxazine series and

U has the abovementioned meaning if W is C₂ -alkylene.

or

c) D is the radical of an organic dyestuff and U is F or a pyridiniumradical which is unsubstituted or substituted by CO₂ H, CONH₂, SO₃ H orC₁ -C₄ -alkyl. if W is C₂ -alkylene.

D is preferably the radical of an organic dyestuff from the mono- orpolyazo, metal complex azo, anthraquinone, phthalocyanine, formazan,azomethine, dioxazine, phenazine, stilbene, triphenylmethane, xanthene,thioxanthone, nitroaryl, naphthoquinone, pyrenequinone orperylenetetracarbimide series.

X is preferably OSO₃ H, SSO₃ H, OCOCH₃, OPO₃ H₂, OSO₂ CH₃, SCN, NHSO₂CH₃, Cl, F, Br, OCOC₆ H₅, OSO₂ --C₆ H₄ CH₃,N(CH₃)₃ ; if W is --CH₂ --, Xis in particular OSO₃ H, Cl, Br, F.

Examples of suitable bridging members B, which may be identical ordifferent, are: ##STR3## in which the asterisk marks the linkage pointwith D,

R has a meaning mentioned under R_(a),

Alk is straight-chain or branched CC₁ -C₆ -alkylene which may beinterrupted by hetero atoms, such as O, S, ##STR4##

Ar is substituted or unsubstituted phenylene or naphthylene and

Alk or Ar can contain further substituents, for example F, Cl, Br, C₁-C₄ -alkyl, C₁ -C₄ -alkoxy, carboxyl or sulpho.

The radical D in formula (1) can be substituted in the usual manner.Examples of further substituents of the radical D are: alkyl groupshaving 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl orbutyl, alkoxy groups having 1 to 4 carbon atoms, such as methoxy,ethoxy, propoxy, isopropoxy or butoxy, acylamino groups having 1 to 8carbon atoms, such as acetylamino, propionylamino or benzoylamino,amino, alkylamino having 1 to 4 carbon atoms, such as methylamino,ethylamino, propylamino, isopropylamino or butylamino, phenylamino,N,N-di-β-hydroxyethylamino, N,N-di-β-sulphato-ethylamino,sulphobenzylamino, N,N-disulphobenzylamino, alkoxycarbonyl having 1 to 4carbon atoms in the alkoxy radical, such as methoxycarbonyl orethoxycarbonyl, alkylsulphonyl having 1 to 4 carbon atoms, such asmethylsulphonyl or ethylsulphonyl, trifluoromethyl, nitro, cyano,halogen, such as fluorine, chlorine or bromine, carbamoyl,N-alkylcarbamoyl having 1 to 4 carbon atoms in the alkyl radical, suchas N-methylcarbamoyl or N-ethylcarbamoyl, sulphamoyl, N-alkylsulphamoylhaving 1 to 4 carbon atoms, such as N-methylsulphamoyl,N-propylsulphamoyl, N-isopropylsulphamoyl or N-butylsulphamoyl,N-(4-hydroxyethyl)sulphamoyl, N,N-di-(β -hydroxyethyl)sulphamoyl,N-phenylsulphamoyl, ureido, hydroxyl, carboxyl, sulphomethyl or sulpho.The radical D preferably contains one or more sulpho groups. Reactivedyestuffs of the formula (1) in which D is the radical of an azodyestuff contain as substituents in particular methyl, ethyl, methoxy,ethoxy, acetylamino, benzoylamino, amino, chlorine, bromine, ureido,hydroxyl, carboxyl, sulphomethyl or sulpho.

The radical R_(a) and R_(b) in formula (1) is, if it is an alkylradical, straight-chain or branched; it can be further substituted, forexample by halogen, hydroxyl, cyano, C₁ -C₄ -alkoxy, carboxyl or sulpho.Examples of R are the following radicals: methyl, ethyl, propyl,isopropyl, butyl, isobutyl, sec.-butyl, tert.-butyl, carboxymethyl,β-carboxyethyl, β-carboxypropyl, methoxycarbonylmethyl,ethoxycarbonylmethyl, β-methoxyethyl, β-ethoxyethyl, β-methoxypropyl,β-chloroethyl, γ-bromopropyl, β-hydroxyethyl, β-hydroxybutyl,β-cyanoethyl, sulphomethyl, β-sulphoethyl, aminosulphonylmethyl andβ-sulphatoethyl.

Examples of suitable bridging members W are ##STR5##

Preferred dyestuffs are those of the formula ##STR6## in which

B, D have the abovementioned meaning

R_(a), identical or different, is H or C₁ -C₂ -alkyl,

R_(b) is H, C₁ -C₃ -alkyl, β-hydroxyethyl, β-sulphatoethyl,β-carboxyethyl, β-cyanoethyl or carboxymethyl,

U is Cl, F or a pyridinium radical which is unsubstituted or substitutedby CO₂ H, CONH₂, SO₃ H or C₁ -C₄ -alkyl,

W is CH₂, C₂ H₄, ##STR7## --(CH₂)₃ -- or --(CH₂)₄ --,

Y is CH═CH₂ or CH₂ --CH₂ --X, where

X is Cl or OSO₃ H

V is H, Cl, C₁ -C₂ -alkyl, C₁ -C₂ -alkoxy, COOH or SO₃ H.

Preferred dyestuffs are those of the formulae (4) to (8) ##STR8## inwhich

R_(a) is H or C₁ -C₂ -alkyl,

Pc is a phthalocyanine ring,

Me is a divalent metal ion, for example Fe, Cu, Zn, Co, Ni, preferablyCu, Ni,

n is 0 or 1,

u+v+w is 3-4, with the proviso that

w is 0.8-2.0,

v is 0-1.0,

u is 1.0-3.0,

A₁ is an aliphatic, araliphatic or aromatic bridging member,

G is oxygen or --N--R₁₁, in which

R₁₁ is H, C₁ -C₂ -alkyl, in which if A₁ is C₂ -alkylene, R₁₁ and R_(a)can be closed to give a ring,

T₁, T₂ are H, chlorine, bromine, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy oracylamino,

R₁ -R₆, independently of one another, are H, C₁ -C₄ -alkyl, C₁ -C₄-alkoxy, hydroxyl, halogen, carboxyl, sulphonamido, alkyl- orarylcarbonylamino or -sulphonylamino, β-sulphatoethylsulphonyl or SO₃ H,

R₇ -R₁₀ are H, C₁ -C₂ -alkyl, which is unsubstituted or substituted byhydroxyl, carboxyl or sulphonyl, in which R₉ and R₁₀ can also be closedto give a ring if A₁ is C₂ -alkylene,

Z is a radical of the formula ##STR9## in which

U is Cl, F or a pyridinium radical which is unsubstituted or substitutedby CO₂ H, CO₂ NH₂, SO₃ H or C₁ -C₄ -alkyl,

A is a radical of the formula ##STR10## in which

R_(b) is H, CH₃, C₂ H₅, i--C₃ H₇, n-C₃ H₇, C₂ -H₄ -OH, carboxymethyl,carboxyethyl or β-cyanoethyl

W is --CH₂ --, --C₂ H₄ --, ##STR11## --(CH₂)₃ --, --(CH₂)₄ --,

V is H, SO₃ H, COOH, C₁ -C₂ -alkyl, C₁ -C₂ -alkoxy, Cl,

Y is CH═CH₂ or CH₂ --CH₂ --X

where X is Cl or OSO₃ H.

Particularly suitable aliphatic radicals A₁ are C₂ -C₈ -alkyl radicals,which may be interrupted by hetero atoms or hetero atom groupings or maybe substituted, such as, for example, ##STR12##

Particularly suitable araliphatic radicals A₁ are C₁ -C₄ -alkylenephenylradicals, which may be interrupted by hetero atoms or hetero atomgroups, such as, for example, ##STR13##

Particularly suitable aromatic radicals A₁ are phenylene radicals, whichmay be substituted by substituents such as, for example C₁ -C₂ -alkyl,SO₃ H or COOH, such as, for example, ##STR14##

Particular preference is given to copper formazan dyestuffs of theformulae (9)-(12) ##STR15## in which

R_(a) is H, C₁ -C₂ -alkyl,

Z has the abovementioned meaning of the formula (2a) and the totalnumber of sulpho groups in the dyestuff is at least 2.

Very particular preference is given to copper formazan dyestuffs of theformula ##STR16## in which

U denotes F, Cl or a pyridinium radical which is unsubstituted orsubstituted by CO₂ H, CO₂ NH₂, SO₃ H or C₁ -C₄ -alkyl,

A denotes ##STR17## in which V, W and R_(b) have the meanings mentionedin formula (3a).

Furthermore, particular preference is given to phthalocyanine dyestuffsof the formula (13) ##STR18## in which

Z, Pc, u, v, w have the abovementioned meaning,

Me is Cu or Ni,

A₁ is C₂ -C₄ -alkylene, 1,3-phenylene, 1,3-sulphophenylene or1,3-carboxyphenylene.

Furthermore, particular preference is given to triphendioxazinedyestuffs of the formulae (14) and (15) ##STR19## in which

Z is the radical of the formula (2a)

R_(a) is H or C₁ -C₂ -alkyl

G is O, N--R₁₁ (where R₁₁ is H, C₁ -C₂ -alkyl, in which if A₁ is C₂ H₄R_(a) and R₁₁ can also be closed to give a ring),

T₁, T₂ are Cl or Br.

Particular preference is also given to anthraquinone dyestuffs of theformula (16) ##STR20## in which

n is 0 or 1

R_(a) is H, C₁ -C₂ -alkyl

Z is the radical of the formula (2a)

R₁₂ is H, C₁ -C₄ -alkyl, alkoxy, halogen, CO₂ H or SO₃ H,

R₁₃ -R₁₅, independently of one another, are H, C₁ -C₄ -alkyl or SO₃ H.

Further preference is given to the azo-dyestuffs of the formula: (II)##STR21## in which

D is the radical of a dyestuff from the mono- or polyazo, metal complexazo series,

B has the abovementioned meaning

R_(a) is H, C₁ -C₂ -alkyl

Z is the radical of the formula ##STR22## in which

A is ##STR23## in which

R_(b) is H, CH₃, C₂ H₅, i--C₃ H₇, n-C₃ H₇, C₂ H₄ OH, carboxymethyl,carboxyethyl

W is --C₂ H₄ --, ##STR24## --(CH₂)₃ --,

V, Y have the meaning given in formula (3a).

Preferred azo-dyestuffs are those of the formulae (17) to (28):##STR25##

R₁₆ is alkyl, alkoxy, halogen,

R₁₇ is H, alkyl, aryl, hetaryl, aralkyl

R₁₈ is COOH, CH₃ ##STR26##

R₁₆ is alkyl, alkoxy, halogen,

R₁₇ is H, alkyl, aralkyl, aryl,

R₁₈ is alkyl, aryl, aralkyl, hetaryl,

R₁₉ is H, COOR₃, ##STR27## CN, CH₂ --SO³, SO₃ H, ##STR28##

R₁₆ is alkyl, alkoxy, halogen

R₂₀ is alkyl, alkoxy, acylamino, amino

o,p are in the o or p position relative to the azo group ##STR29##

R₁₆ is alkyl, alkoxy, halogen

R₂₀ is alkyl, alkoxy, arylamino

o, p are the ortho or para position relative to the azo group

R₂₁ is H, C₁ -C₂ -alkyl, acylamino, ureido

R₂₂ is R₈, NO₂ ##STR30##

R₁₆ is alkyl, alkoxy, halogen

K is the radical of a coupling component, suitable coupling componentsbeing in particular those from the pyridone, pyrazolone, aceto acidarylide and naphtholsulphonic acid series. ##STR31## where

R₂₃ is alkyl, halogen

R₁₆ is alkyl, alkoxy

K is the radical of a coupling component ##STR32##

R₁₆ is alkyl, alkoxy, arylamino ##STR33##

R₁₆ is alkyl, alkoxy

R₂₄ is H, NH₂, arylamino.

The present invention also relates to the preparation of the reactivedyestuffs of the formula (1) by methods known per se.

The following may be mentioned:

1. Preparation of the reactive dyestuffs takes place by condensing adyestuff base of the general formula

    D-B-NR.sub.a -H                                            (29)

in which D, B and R_(a) have the abovementioned meaning with2,4,6-trichloro- or 2,4,6-trifluorotriazine.

The intermediate is converted in a further reaction step with anaminosulphone of the formula ##STR34## in which R_(b), V, Y and W havethe abovementioned meaning, into the reactive dyestuff.

2. Preparation of the dyestuffs of the formula (1) can also take placeby condensing a dyestuff base of the general formula (29), in which Dhas the abovementioned meaning, with the fibre-reactive compound of theformula (31). ##STR35##

W, U, R_(b), V and Y have the abovementioned meanings.

3. Suitable dyestuff precursors are condensed with trihalogenotriazinesand the components of the formula (30) or suitable precursors arecondensed with the primary condensation products of the formula (31) andthen converted into the dyestuff.

4. If desired, the halogen atom in the synthesised halogenotriazinedyestuff is exchanged for the radical of a pyridine which may besubstituted by COOH, CONH₂, SO₃ H, C₁ -C₄ -alkyl.

The condensations of the starting components with thetrihalogenotriazines and the components of the formula (30) or with thereactive components of the formula (31) are carried out, irrespective ofthe order, in aqueous or organic-aqueous media in the presence ofacid-binding agents. The first step of the condensation is carried out,depending on the nature of the starting components, in pH ranges from 2to 8, preferably 3 to 7, and at temperatures from 0° to 40° C.,preferably 0° to 25° C. The exchange of the second halogen atom of thetriazine is completed in a pH range from 4 to 10, preferably 5 to 9, andin a temperature range from 0° to 60° C., preferably 0° to 30° C.

Examples of acid-binding agents are carbonates, hydroxides orphosphates, such as sodium carbonate, sodium bicarbonate, dilute sodiumhydroxide solution, di- or trisodium phosphate or sodium fluoride.

If the condensation or the dyestuff synthesis is intended to leaddirectly to a dyestuff solution or to a liquid dyestuff preparation, theuse of lithium carbonate or lithium hydroxide may be advantageous,possibly together with solubilisers and/or stabilising buffer systems.Other conversion reactions of the dyestuffs or precursors thereof, suchas metallisation reactions, sulphonations or introduction of acylaminogroupings can in general be carried out during any desired steps of thedyestuff syntheses.

Particularly valuable dyestuffs of this series are water-solubleformazan, anthraquinone, triphendioxazine and phthalocyanine and azodyestuffs, and in particular those having sulpho and/or carboxyl groups.The dyestuffs can be either metal-free or metal-containing, the metalcomplexes which are preferred being the copper complexes, nickelcomplexes, chromium complexes and cobalt complexes.

Suitable dyestuff radicals D or amino-containing dyestuff bases on whichthe dyestuffs of the formula (1) are based have been described in theliterature in very large numbers. Examples are:

    ______________________________________                                        German Auslegeschrift 2,557,141                                                                      Dyestuff bases of                                                             the formulae 9-11                                      German Auslegeschrift 3,239,364 A1                                                                   Dyestuff bases of                                                             the formula 12                                         German Offenlegungsschrift 164,463                                                                   Dyestuff bases of                                      US 4,007,164           the formula 13                                         German Offenlegungsschrift 2,503,011                                                                 Dyestuff bases of                                      German Offenlegungsschrift 2,124,080                                                                 the formulae                                           German Offenlegungsschrift 3,423,581                                                                 14-15                                                  U. Venkataraman        Dyestuff bases of                                      "The Chemistry of Synthetic                                                                          the formula 16                                         Dyes", Vol. III, Academic Press,                                              New York, 1952                                                                ______________________________________                                    

Further examples are mentioned in the following publications: EP-A54,515, EP-A 69,703, EP-A 70,807, EP-A 73,267, German Auslegeschrift3,222,726, German Auslegeschrift 2,557,141, German Auslegeschrift2,650,555, German Auslegeschrift 3,023,855, German Auslegeschrift2,847,938, German Auslegeschrift 2,817,780, GB-A 2,057,479, GermanAuslegeschrift 2,916,715, German Auslegeschrift 2,814,206, GermanAuslegeschrift 3,019,936, EP-A 45,488 and Venkataraman: The Chemistry ofSynthetic Dyes, Vol. VI, Chapter II, p. 211-325, New York, London; 1972.

The invention also relates to the new amines of the formula ##STR36## inwhich

M is C₂ H₅, C₃ H₇, C₂ H₅ OH,

V¹ is H, Cl, SO₃ H, CH₃, CO₂ H, OCH₃,

L is CH═CH₂, CH₂ --CH₂ --Q,

Q is Cl, OH, --OSO₃ H,

W¹ is CH₂, C₂ H₄, ##STR37##

The new amines of the formula (32) are prepared by methods known per se:

Nitro- or acylamino compounds of the formula (33) ##STR38## in which

V¹, W¹ have the abovementioned meaning,

E is NO₂ or acylamino,

Y¹ is Cl, Br, --OSO₃ H, ##STR39## O--SO₂ --CH₃ are reacted in a mannerknown per se with 2-mercaptoethanol to give sulphides of the formula##STR40## in which

E, V¹ and W¹ have the abovementioned meaning,

these sulphides are then oxidised in a known manner, for example with H₂O₂ or chlorine, to sulphones of the formula (35) ##STR41## in which

V¹, W¹ have the abovementioned meaning,

and the nitro group E is then reduced or the acylamino group E ishydrolysed. The resulting known amino compounds of the formula (36)##STR42## in which

V¹, W¹ have the abovementioned meaning,

Q¹ is HO or Cl,

are N-alkylated in a known manner (for example by reductive alkylation).If desired, the OH group in Q¹ is subsequently converted into an --OSO₃H group (in a known manner using sulphuric acid or oleum). By thereaction with oleum, it is additionally possible to introduce, apartfrom the sulphato groups, sulpho groups (V¹ =SO₃ H) into the phenyleneradical. The amines thus obtained can be converted into compounds of theformula (32), in which the grouping L is the grouping --CH═CH₂, bytreatment with alkaline agents, such as alkali metal hydroxide or alkalimetal carbonate.

Compounds of the formula (35) where E is NO₂ can also be synthesisedstarting from compounds of the formula ##STR43## in which

W¹, Y¹ have the abovementioned meaning and

V² is H, C₁ -C₂ -alkyl,

by reaction with 2-mercaptoethanol, followed by oxidation to give thecompounds of the formula ##STR44## in which

V², W¹, Q¹ have the abovementioned meaning

and subsequent nitration of the compounds (38) to give compounds of theformula (35) where E is NO₂. Any OH groups Q¹ esterified duringnitration can be reconverted into OH groups by hydrolysis. When thenitro group is introduced via the compounds of the formula (38),mixtures of isomers W¹ --SO₂ --CH₂ --CH₂ --Q¹ are generally formed withrespect to the position of the nitro group relative to the side chain.

An important and specific variant for preparing the compounds of theformula (38) or (35) is the free radical catalysed addition reaction of2-mercaptoethanol with styrenes or allylbenzenes of the formula##STR45## where

E¹ is H, NO₂,

R_(c), R_(d) are H, C₁ -C₂ -alkyl, and

V² has the abovementioned meaning,

subsequent oxidation of the sulphides formed of the formula ##STR46##where E¹, V², R_(c), R_(d) have the meanings mentioned to give sulphonesof the formula ##STR47## in which

E¹, V², R_(c), R_(d) have the abovementioned meaning, and

Q¹ is OH, Cl

and, if desired, subsequent nitration, i.e. conversion of E¹ =H to E¹=NO₂ to give the compounds of the formula (35).

In a further preferred embodiment, the invention relates to a processfor the preparation of amines according to claim 11 (where W is C₂ H₄),characterised in that an addition reaction of 2-mercaptoethanolcatalysed by free radicals with ethenyl aromatics of the formula (33a)##STR48## in which

E¹ is H, NO₂ or acylamino, and

V¹ has the meaning given in formula (33)

is carried out to give sulphides of the formula (34a) ##STR49## thesesulphides are oxidised to the sulphones of the formula ##STR50## inwhich

Q¹ is OH or Cl,

and then, if E¹ is H,

E¹ is nitrated to NO₂, the nitro group E¹ is reduced or the acylaminogroup E¹ is hydrolysed and the resulting amino compounds are, ifdesired, N-alkylated and/or the OH group Q¹ is converted into an OSO₃ Hgroup and, if desired, an SO₃ H group is introduced on the phenyl ringinstead of V¹ ═H.

Particularly suitable amines of the formula (30) for reaction with2,4,6-trichloro- or 2,4,6-trifluorotriazine or with a precondensationproduct of the dyestuff bases of the formula (29) with theabovementioned triazine are, for example: ##STR51##

The dyestuffs according to the invention are highly suitable for thedyeing and printing of natural and synthetic hydroxyl- oramido-containing materials, in particular those consisting of celluloseand polyamide. Dyestuff mixtures composed of dyestuffs of the formula(1) have improved solubility properties.

The dyestuffs as well as the dyestuff mixtures are particularly suitablefor the dyeing of cellulose materials by the exhaust, padding, coldpad-batch and continuous methods, and for printing.

The dyestuffs according to the invention, in particular those of thegeneral formula (1), are highly suitable in mixtures with otherdyestuffs, in particular for trichromatic dyeing.

The reactive dyestuffs of the formula (1) are distinguished by highreactivity and excellent fixation powers. Owing to theirbifunctionality, they produce high fixation yields even from a longliquor. They are characterised by a relative independence of the yieldfrom the dyeing temperature and can therefore be used in the exhaustmethod at low to medium dyeing temperatures. In the pad-steam process,they require only short steaming times. They produce dyeings of highcolour strength and good light and wet fastness properties.

The dyestuff formulae given are those of the free acids. In general, thesalts are obtained in the preparation, in particular the alkali metalsalts, such as sodium salts, potassium salts or lithium salts. Thedyestuffs can also be used as concentrated solutions.

EXAMPLE 1

65 g of the sodium salt of the compound of the formula ##STR52## aredissolved in 200 ml of water at a pH of 7.5. The solution is cooled to0° C. and 9 g of trifluorotriazine are added dropwise over a period of20 minutes, while maintaining the pH at 6-7 by adding sodium carbonatesolution. After conversion is complete, a neutralised solution of 17.5 gof 4-aminobenzyl β-sulphatoethyl sulphone in 100 ml of water is addeddropwise and the pH is maintained at 7 with sodium carbonate solution.After condensation is complete, the dyestuff is isolated either byevaporation or spray-drying or by salting out. The dyestuff thusobtained of the formula ##STR53## dyes cotton in blue hues which havegood fastness properties.

EXAMPLE 2

A further valuable dyestuff is obtained by repeating the procedure ofExample 1, using the sodium salt of the compound of the formula##STR54## instead of the dyestuff base used in Example 1. The dyestuffthus obtained of the formula ##STR55## dyes cotton in blue hues whichhave good fastness properties.

EXAMPLE 3

The procedure of Example 1 is repeated, using 4-[N-ethyl]aminobenzyl(β-sulphatoethyl) sulphone instead of 4-aminobenzyl (β-sulphatoethyl)sulphone, to give the dyestuff of the formula ##STR56## which dyescotton, by the application methods customary for reactive dyestuffs, inblue hues.

EXAMPLE 4

The procedure of Example 3 is repeated, using 2,4,6-trichlorotriazineinstead of 2,4,6-trifluorotriazine, to give a dyestuff of the formula##STR57## which dyes cotton, by dyeing methods customary for reactivedyestuffs, in blue hues.

EXAMPLES 5 TO 41

Further valuable dyestuffs according to the invention are obtained bythe procedure of Example 1 by reacting the components listed in Table 1.

The dyestuffs obtained have very good fibre-reactive dyestuff propertiesand produce by the customary dyeing and printing processes dyeings andprints of high colour strength and good fastness properties in the hueon cotton listed in the particular table example.

                                      TABLE 1                                     __________________________________________________________________________     ##STR58##                                                                    Ex.                                                                              R.sub.1                                                                           R.sub.2                                                                           Hal                                                                              A                       Hue                                                                              λmax                          __________________________________________________________________________     5 SO.sub.3 H                                                                        H   F                                                                                 ##STR59##              blue                                                                             613 nm                                6 SO.sub.3 H                                                                        H   Cl                                                                                ##STR60##              blue                                                                             613 nm                                7 SO.sub.3 H                                                                        H   F                                                                                 ##STR61##              blue                                                                             614 nm                                8 SO.sub.3 H                                                                        H   F                                                                                 ##STR62##              blue                                                                             612 nm                                9 SO.sub.3 H                                                                        H   F                                                                                 ##STR63##              blue                                                                             610 nm                               10 SO.sub.3 H                                                                        H   F                                                                                 ##STR64##              blue                                                                             615 nm                               11 SO.sub.3 H                                                                        H   Cl                                                                                ##STR65##              blue                                    12 SO.sub.3 H                                                                        H   F                                                                                 ##STR66##              blue                                    13 SO.sub.3 H                                                                        H   F                                                                                 ##STR67##              blue                                    14 SO.sub.3 H                                                                        H   F                                                                                 ##STR68##              blue                                    15 SO.sub.3 H                                                                        H   F                                                                                 ##STR69##              blue                                    16 SO.sub.3 H                                                                        H   Cl                                                                                ##STR70##              blue                                    17 SO.sub.3 H                                                                        H   F                                                                                 ##STR71##              blue                                    18 SO.sub.3 H                                                                        H   F                                                                                 ##STR72##              blue                                    19 SO.sub.3 H                                                                        H   Cl                                                                                ##STR73##              blue                                    20 SO.sub.3 H                                                                        H   F                                                                                 ##STR74##              blue                                    21 SO.sub.3 H                                                                        H   F                                                                                 ##STR75##              blue                                                                             614 nm                               22 SO.sub.3 H                                                                        H   F                                                                                 ##STR76##              blue                                                                             613 nm                               23 SO.sub.3 H                                                                        H   F                                                                                 ##STR77##              blue                                    24 SO.sub.3 H                                                                        H   F                                                                                 ##STR78##              blue                                    25 SO.sub.3 H                                                                        H   Cl                                                                                ##STR79##              blue                                    26 SO.sub.3 H                                                                        H   F                                                                                 ##STR80##              blue                                    27 SO.sub.3 H                                                                        H   F                                                                                 ##STR81##              blue                                    28 SO.sub.3 H                                                                        H   Cl                                                                                ##STR82##              blau                                    29 SO.sub.3 H                                                                        H   F                                                                                 ##STR83##              blue                                    30 SO.sub.3 H                                                                        H   F                                                                                 ##STR84##              blue                                                                             612 nm                               31 SO.sub.3 H                                                                        H   Cl                                                                                ##STR85##              blue                                     31a                                                                             SO.sub.3 H                                                                        H   F                                                                                 ##STR86##              blue                                                                             614 nm                                31b                                                                             SO.sub.3 H                                                                        H   F                                                                                 ##STR87##              blue                                                                             612 nm                                31c                                                                             SO.sub.3 H                                                                        H   F                                                                                 ##STR88##              blue                                                                             611 nm                               32 H   SO.sub.3 H                                                                        F                                                                                 ##STR89##              blue                                                                             617 nm                               33 H   SO.sub.3 H                                                                        F                                                                                 ##STR90##              blue                                                                             618 nm                               34 H   SO.sub.3 H                                                                        F                                                                                 ##STR91##              blue                                                                             616 nm                               35 H   SO.sub.3 H                                                                        F                                                                                 ##STR92##              blue                                                                             616 nm                               36 H   SO.sub.3 H                                                                        F                                                                                 ##STR93##              blue                                                                             616 nm                               37 H   SO.sub.3 H                                                                        F                                                                                 ##STR94##              blue                                                                             618 nm                               38 H   SO.sub.3 H                                                                        F                                                                                 ##STR95##              blue                                                                             617 nm                                38a                                                                             H   SO.sub.3 H                                                                        F                                                                                 ##STR96##              blue                                                                             618 nm                               39 H   SO.sub.3 H                                                                        F                                                                                 ##STR97##              blue                                    40 H   SO.sub.3 H                                                                        F                                                                                 ##STR98##              blue                                    41 H   SO.sub.3 H                                                                        F                                                                                 ##STR99##              blue                                    __________________________________________________________________________

EXAMPLES 42 TO 50

Further dyestuffs according to the invention of the general formula##STR100## are obtained analogously to the exemplary embodiment byreacting the components listed in Table 2.

The dyestuffs obtained have very good fibre-reactive dyestuff propertiesand produce by the customary dyeing and printing processes dyeings andprints of high colour strength and good fastness properties in the hueon cotton listed in the particular table example.

    TABLE 2      Ex. R.sub.1 R.sub.2 R.sub.3 R.sub.4 R.sub.5 A Hue               42 SO.sub.3 H H SO.sub.3      H     ##STR101##      SO.sub.3      H     ##STR102##      reddish blue  42a SO.sub.3 H H SO.sub.3      H     ##STR103##      SO.sub.3      H     ##STR104##      reddish blue  42b SO.sub.3 H H SO.sub.3      H     ##STR105##      SO.sub.3      H     ##STR106##      reddish blue  42c SO.sub.3 H H SO.sub.3      H     ##STR107##      SO.sub.3      H     ##STR108##      blue  43 SO.sub.3      H H H     ##STR109##      SO.sub.3      H     ##STR110##      blue  43a SO.sub.3      H H H     ##STR111##      SO.sub.3      H     ##STR112##      blue  43b SO.sub.3      H H H     ##STR113##      SO.sub.3      H     ##STR114##      blue  43c SO.sub.3      H H H     ##STR115##      SO.sub.3      H     ##STR116##      blue  43d SO.sub.3      H H H     ##STR117##      SO.sub.3      H     ##STR118##      blue  43e SO.sub.3      H H H     ##STR119##      SO.sub.3      H     ##STR120##      blue  44 H SO.sub.3 H SO.sub.3      H     ##STR121##      SO.sub.3      H     ##STR122##      reddish blue  45 H SO.sub.3      H H     ##STR123##      SO.sub.3      H     ##STR124##      blue      46 H     ##STR125##      SO.sub.3 H SO.sub.3 H SO.sub.3      H     ##STR126##      blue      47     ##STR127##      H SO.sub.3 H SO.sub.3 H SO.sub.3      H     ##STR128##      reddish blue  48 H SO.sub.3 H SO.sub.3 H SO.sub.3      H     ##STR129##      ##STR130##      reddish blue  49 H SO.sub.3      H     ##STR131##      SO.sub.3      H H     ##STR132##      greenish blue  50 H SO.sub.3 H SO.sub.3 H SO.sub.3      H     ##STR133##      ##STR134##      reddish blue  50a H SO.sub.3 H SO.sub.3 H SO.sub.3      H     ##STR135##      ##STR136##      reddish blue  50b H SO.sub.3 H SO.sub.3 H SO.sub.3      H     ##STR137##      ##STR138##      reddish blue  50c SO.sub.3 H H SO.sub.3 H SO.sub.3      H     ##STR139##      ##STR140##      reddish blue  50d SO.sub.3 H H SO.sub.3 H SO.sub.3      H     ##STR141##      ##STR142##      reddish blue  50e SO.sub.3 H H SO.sub.3 H SO.sub.3      H     ##STR143##      ##STR144##      reddish blue

EXAMPLE 51

32.9 g of copper phthalocyanine compound of the formula ##STR145##prepared by condensation of copper phthalocyaninetetra-(sulphochloride-sulphonic acid) with 3-aminoacetanilide andammonia, followed by hydrolysis of the acetylamino group in dilutesodium hydroxide solution at 75° C. are dissolved in 420 ml of water ata pH of 7. The solution is added dropwise over a period of 30 minutes toa suspension prepared from a solution of 5.9 g of cyanuric chloride in50 ml of acetone and 50 g of ice, and the temperature of the reactionmixture is maintained at 0° to 3° C., and the pH at 4.0 to 4.5 bymetering in 2N sodium carbonate solution. 30 minutes after addition iscomplete, the resulting solution is clarified and 10.7 g of4-aminobenzyl β-sulphatoethyl sulphone are added. The condensation iscarried out at the pH of 6.0 to 6.5 by further addition of sodiumcarbonate solution and at 15° to 23° C. The dyestuff obtained isisolated either by evaporation or spray-drying or by salting out using70 g of sodium chloride and filtration of the solution. It has theformula ##STR146## and dyes cotton from a long liquor or by the knownpadding process in greenish blue hues.

A similar dyestuff is obtained by repeating the procedure, using 33.9 gof copper phthalocyanine compound of the formula ##STR147## instead ofthe dyestuff base used at the beginning. The dyestuff thus obtained hasan absorption of λmax of 668 nm, 629 nm in H₂ O.

EXAMPLE 52

28.3 g of the copper phthalocyanine compound of the formula ##STR148##prepared by condensation of copper phthalocyaninetetra-(sulphochloride-sulphonic acid) with monoacetylethylenediamine,followed by hydrolytic cleavage of the acetyl radical with dilute sodiumhydroxide solution at 75° C. are dissolved in 380 ml of water at a pH of8.5. The solution is added dropwise over a period of 30 minutes to asuspension obtained by pouring a solution of 7.2 g of cyanuric chloridein 45 ml of acetone onto 45 g of ice. The pH of the reaction mixture iskept at 7.0 to 7.5 by adding 2N sodium hydroxide solution and thetemperature is kept at 0° to 5° C. After stirring is continued for 1hour, the solution is clarified, and 11.5 g of 4-aminobenzylβ-sulphatoethyl sulphone are added in portions to the filtrate. Whilethe sulphone is sprinkled in and after that, the pH of the reactionmixture is kept at 6.0 to 6.5 and the temperature is increased first to20° to 25° C. and after 2 hours to 30° C.

After condensation is complete, the dyestuff is salted out from thesolution using sodium chloride, filtered off with suction and dried at50° C. in vacuo. It has the formula ##STR149## and produces on cottongreenish blue dyeings and prints.

Similar dyestuffs are obtained by using 28.4 g of the copperphthalocyanine compound of the formula ##STR150## or 33.7 g of thecopper phthalocyanine compound of the formula ##STR151## instead of theabove copper phthalocyanine compound.

EXAMPLE 53

10.9 g of 4-aminobenzyl β-sulphatoethyl sulphone are dissolved in 150 mlof water at a pH of 5.5. 0.3 g of sodium fluoride is added to thesolution, and the mixture is cooled to 0°-3° C. 6.1 g of cyanuricfluoride is run in with thorough stirring, and the pH is maintained at4.5 using dilute sodium carbonate solution. After stirring is continuedfor a short period, condensation is complete.

32 g of the copper phthalocyanine component of the formula ##STR152##prepared by the details given in European Patent Specification 0,073,267are dissolved in 300 ml of water at a pH of 7.0-7.5. The solution of theabove condensation product is then run into the dyestuff component at0°-5°, and the pH in the reaction mixture is maintained at 7.0 to 7.5.After 3 hours, the temperature is allowed to increase gradually to 20°C. and the pH is still kept constant. After reaction is complete, theproduct obtained is salted out from the solution, filtered off withsuction, buffered with a small amount of phosphate solution at a pH of6.0 and dried at 45° C. in vacuo. The dyestuff has the formula##STR153## and dyes cotton from a long liquor and by the knowncontinuous process in greenish blue hues.

Further phthalocyanine reactive dyestuffs are obtained by condensing themetal phthalocyanine components and reactive components mentioned inTable 3 in an analogous manner.

                                      TABLE 3                                     __________________________________________________________________________    Ex.                                                                              Phthalocyanine component                                                                             Reactive component              Hue                 __________________________________________________________________________    54                                                                                ##STR154##                                                                                           ##STR155##                     greenish blue       55                                                                                ##STR156##                                                                                           ##STR157##                     bluish green                                   ##STR158##                                         56                                                                                ##STR159##                                                                                           ##STR160##                     bluish green        57                                                                                ##STR161##                                                                                           ##STR162##                     bluish green        58                                                                                ##STR163##                                                                                           ##STR164##                     greenish blue                                  ##STR165##                                         59                                                                                ##STR166##                                                                                           ##STR167##                     greenish blue                                  ##STR168##                                         60                                                                                ##STR169##                                                                                           ##STR170##                     greenish blue                                  ##STR171##                                         __________________________________________________________________________

EXAMPLE 61

40 g of1-amino-4-(2'-aminomethyl-4'-methyl-6'-sulphophenylamino)-anthraquinone-2-sulphonicacid are dissolved in 800 ml of water and 100 ml of acetone at a pH of 7by neutralisation with about 45 ml of 2N sodium hydroxide solution. Themixture is cooled to 10° C., and a solution of 17.5 g of cyanuricchloride in 100 ml of acetone is added dropwise over a period of 15 to20 minutes. During the dropwise addition, the pH in the reaction mixtureis maintained at 6.0 to 7.0 with 2N sodium carbonate solution. When,about 1 hour after the addition of cyanuric chloride, sodium carbonateconsumption has come to a standstill, a neutralised solution of 26.6 gof 4-aminobenzyl β-sulphatoethyl sulphone in 270 ml of water is run inat 20° C., the pH is maintained at 6.5 with sodium carbonate solutionand the temperature is increased to 25°-30°. After condensation iscomplete, the dyestuff is precipitated by salting out, isolated anddried at 50° C. in vacuo. It has the formula ##STR172## and produces oncellulose fibres by the known padding and printing processes brilliantreddish blue dyeings and prints.

EXAMPLE 62

53.1 g of1-amino-4-(3'-amino-5'-sulpho-2',4',6'-trimethylphenylamino)-anthraquinone-2-sulphonicacid are dissolved in 530 parts of water at a pH of 6. 19.4 g ofcyanuric chloride are dissolved in 100 ml of methyl ethyl ketone and thesolution is poured onto 100 g of ice. The dyestuff solution is thenadded dropwise to the cyanuric chloride suspension at 0°-10° C. and thepH in the reaction mixture is maintained at 4.5 with 10% strength sodiumcarbonate solution. After reaction is complete, a neutralised solutionof 31.0 g of 4-aminobenzyl β-sulphatoethyl sulphone in 310 ml of waterare metered in and the pH is maintained at 5.8 to 6.0 with dilute sodiumcarbonate solution at a temperature of 20°-25° C. until condensation iscomplete. The dyestuff obtained of the formula ##STR173## is isolated bysalting out and filtration and dried at 50° C. in vacuo.

It produces on cotton brilliant reddish blue dyeings and prints.

A similar dyestuff is obtained by using the same amount of 3-aminobenzylβ-sulphatoethyl sulphone instead of the 4-aminobenzyl β-sulphatoethylsulphone.

EXAMPLE 63

14.7 g of 1-amino-4-(3'-aminophenylamino)anthraquinone-2,4'-disulphonicacid are dissolved in 250 ml of water at a pH of 5 and 0°-5° C. 2.8 mlof cyanuric fluoride are added dropwise to the solution of the dyestuffcomponent over a period of 5 to 10 minutes, and the pH is maintained at4.2 to 4.7 with 2N sodium carbonate solution. After stirring iscontinued for a short period, condensation to give the difluorotriazinyldyestuff is complete.

9.8 g of 4-aminobenzyl β-sulphatoethyl sulphone are slowly added to thesolution of the reactive dyestuff component, while maintaining the pH at5.0 to 5.6. The pH is then maintained at 6.0 to 6.5 and the temperatureis increased gradually to 20° C. over a period of 15 hours, after whichcondensation is complete. The dyestuff is then salted out using 8% ofpotassium chloride over a period of 2 hours. The precipitated dyestuffof the formula ##STR174## is filtered off with suction and washed with10% strength potassium chloride solution until the runoff remains clear.Drying at 45° C. in vacuo gives a product with which cellulose fabriccan be dyed and printed in blue hues.

EXAMPLE 64

13.2 g of 4-aminobenzyl β-sulphatoethyl sulphone are dissolved in 250 mlof water. After cooling the solution to 0°-5° C., the pH is brought to4.5. 4.2 ml of cyanuric fluoride are added dropwise to the solution overa period of 15 minutes, and the pH is maintained at 4.0 to 4.5 using 2Nsodium carbonate solution. A neutralised solution of 19.0 g of1-amino-4-(3'-amino-2'-methylphenylamino)-anthraquinone-2,5'-disulphonicacid in 350 ml of water is added dropwise to the suspension of thereactive component obtained over a period of 30 minutes. During thisaddition, the temperature in the reaction solution is further maintainedat 0° to 5° C. and the pH at 6.0 to 6.5 with sodium carbonate solution.After 2 hours, the temperature is allowed to increase gradually to 10°C. over a period of 15 hours. After condensation is complete, thedyestuff of the formula ##STR175## is salted out from the solution using10% sodium chloride, filtered off with suction, washed with 10% strengthsodium chloride solution and dried at 45° C. in vacuo.

The dyestuff can be used to dye and print cellulose fibres in clear bluehues.

EXAMPLE 65

If in Example 64 a neutralised solution of 20.4 g of1-amino-4-(4'-methyl-aminomethyl-phenylamino)-anthraquinone-2,2'-disulphonicacid is reacted, instead of the anthraquinone component listed there,with the condensation product of 13.6 g of 4-aminophenyl β-sulphatoethylsulphone with 4.4 ml of cyanuric fluoride at 0° to 5° C. and a pH of 6.5to 7.0, and the product is worked up as described there, a dyestuff ofthe formula ##STR176## is obtained, which likewise produces on cotton bythe customary techniques clear blue dyeings and prints.

EXAMPLE 66

9.6 g of cyanuric chloride are dissolved in 50 ml of acetone. Thesolution is poured onto 50 g of ice, and a neutralised solution of 14.8g of 4-aminobenzyl β-sulphatoethyl sulphone in 200 ml of water is thenadded dropwise. Condensation is carried out by dropwise addition of 10%strength sodium carbonate solution at a pH of 4.5 to 4.7, whilemaintaining the temperature at 0°-5° C. and, after condensation iscomplete, at 15°-20° C.

17.6 g of the triphendioxazine compound of the formula ##STR177## aredissolved in 600 ml of water by bringing the pH to 9 using 2N sodiumhydroxide solution. The above reactive component is then added inportions to the solution, and the pH in the reaction mixture ismaintained at 8.5 to 8.7 with 2N sodium hydroxide solution and thetemperature at 15° to 20° C. After reaction is complete, the dyestuff ofthe formula ##STR178## is salted out, filtered off with suction anddried at 50° C. in vacuo. It produces strong blue dyeings on cotton bythe known dyeing techniques.

Further triphendioxazine reactive dyestuffs are obtained by reacting thefollowing components:

      Ex. Triphendioxazine Reactive component Hue          67     ##STR179##      ##STR180##      blue      68     ##STR181##      ##STR182##      blue

EXAMPLE 69

27.3 g of 3,9-diamino-6,13-dichloro-triphendioxazine-4,11-disulphonicacid are dissolved in 900 ml of water by neutralisation with 10%strength lithium hydroxide solution. After cooling the solution to 0°-5°C., 10.8 g of cyanuric fluoride are added dropwise, and the pH ismaintained at 5.5 to 6.0 with 10% strength lithium hydroxide solution.After reaction is complete, 23.6 g of 4-aminobenzyl β-sulphatoethylsulphone are added in portions to the solution and the pH is furtherkept at 6.0 to 6.5. After 5 hours, the temperature is allowed toincrease overnight to 20°-25° C. with further pH control. The solutionis clarified with the addition of 1 g of kieselguhr, the dyestuff issalted out from the filtrate by adding 15% sodium chloride, filtered offwith suction, washed with 15% strength sodium chloride solution anddried at 50° C. in vacuo.

The dyestuff of the formula ##STR183## dyes cotton in strongly reddishblue hues.

EXAMPLE 70

Analogously to Example 69, the following triphendioxazine dyestuff##STR184## is obtained.

It dyes cotton in strongly reddish blue hues.

EXAMPLE 70 a

3.0 g of pyridine-3-carboxylic acid are added to a dyestuff solutionsynthesised according to Example 1. The solution is heated to 75°-80°and the pH is brought to 7.0 using 2N sodium carbonate solution untilexchange of the fluorine atom for the nicotinic acid radical iscomplete. After cooling, the dyestuff can be salted out or the solution,after desalting and concentration, can be used as liquid dyestuff.

The dyestuff has the formula ##STR185## and dyes cotton from a longliquor similarly to the dyestuff from Example 1.

Similarly, the other fluoro- or chlorotriazine dyestuffs described inthe previous examples can also be converted into the 3-carboxypyridiniumtriazine dyestuffs.

EXAMPLE 71

10 g of 4-aminobenzyl β-hydroxyethyl sulphone (prepared according to GB877,250 [C.A. 56; 11758i]), after addition of 3.5 g of acetaldehyde and4 g of Raney nickel, are put under a hydrogen pressure of 60 to 80 barin an autoclave in 100 ml of methanol. The autoclave is heated to 40° C.and the hydrogen pressure is maintained until the reaction is complete.100 ml of methanol are added to the contents of the autoclave, and thesuspension is clarified while boiling hot by filtering off the nickel.Upon concentrating the filtrate, the amine of the formula ##STR186##crystallises, is filtered off with suction from the cooled mixture andcan be washed with a small amount of cold methanol.

¹ H - NMR in D₆ -DMSO (TMS as internal standard):

δ=1.17 (t, 3H), 3.03 (m, 4H), 3.79 (q, 2H), 4.21 (s, 2H), 5.16 (t, NH),5.61 (t, OH), 6.57 (d, 2H), 7.09 (d, 2H) ppm.

EXAMPLE 72

Example 71 is repeated, using 5-amino-2-chlorobenzyl β-hydroxyethylsulphone (prepared according to EP 307,817 A1) instead of 4-aminobenzylβ-hydroxyethyl sulphone to give the amine of the formula ##STR187##

¹ H - NMR in D₆ -DMSO (TMS internal standard):

δ=1.18 (t, 3H), 3.01 (q, 2H), 3.24 (t, 2H), 3.83 (t, 2H), 4.56 (s, 2H),6.59 (dd, 1H), 6.77 (d, 1H), 7.19 (d, 1H) ppm.

EXAMPLE 73

3-Aminobenzyl β-hydroxyethyl sulphone can be converted, instead of4-aminobenzyl β-hydroxyethyl sulphone used in Example 71, by the sameprocess to the amine of the formula ##STR188##

¹ H - NMR in D₆ -DMSO (TMS as internal standard):

δ=1.18 (t, 3H), 3.05 (m, 2H), 3.14 (t, 2H), 3.81 (t, 2H), 4.31 (s, 2H),5.22 (br., NH), 5.62 (t, OH), 6.55 (m, 3H) 7.08 (t, 1H) ppm.

The following compounds are obtained analogously: ##STR189##

¹ H - NMR in D₆ -DMSO (TMS as internal standard):

δ=1.13 (t, 3H), 2.95 (q, 2H), 3.11 (t, 2H), 3.65 (s, 3H), 3.75 (q, 2H),4.26 (s, 2H), 5.00 (t, OH), 5.15 (br., NH), 6.46 (dd, 1H), 6.51 (d, 1H),6.76 (d, 1H) ppm. ##STR190##

¹ H - NMR in D₆ -DMSO (TMS as internal standard):

δ=1.18 (t, 3H), 2.20 (s, 3H), 3.00 (m, 2H), 3.26 (t, 2H), 3.84 (q, 2H),4.40 (s, 2H), 5.20 (t, NH), 5.40 (t, OH), 6.46 (dd, 1H), 6.54 (d, 1H),6.92 (d, 1H) ppm.

EXAMPLE 74

Alkylation can also be carried out using propionaldehyde instead ofacetaldehyde used in Example 72. In this case an amine of the formula##STR191## is obtained.

¹ H - NMR in D₆ -DMSO (TMS as internal standard):

δ=0.95 (t, 3H), 1.55 (q, 2H), 2.92 (q, 2H), 3.24 (t, 2H), 3.81 (q, 2H),4.50 (s, 2H), 5.19 (t, NH), 5.87 (t, OH), 6.58 (dd, 1H), 6.71 (d, 1H),7.14 (d, 1H) ppm.

The following compounds are obtained analogously: ##STR192##

EXAMPLE 75

30 g of 4-[N-ethyl]aminobenzyl β-hydroxyethyl sulphone from Example 71are introduced into 90 ml of 100% pure sulphuric acid at 0° to 10° C.The mixture is stirred for 2 hours and the solution obtained isintroduced into 350 g of ice. The crystalline precipitate is filteredoff with suction, washed with 25% strength sodium chloride solutionuntil the filtrate is free of sulphate and dried at 50° C. in vacuo. Theproduct obtained has the formula ##STR193##

¹ H - NMR in D₆ -DMSO (TMS as internal standard):

δ=1.22 (t, 3H), 3.35 (m, 4H), 4.18 (t, 2H), 4.56 (s, 2H), 7.58 (m, 4H),9.48 (br, NH) ppm.

The following amines are obtained analogously: ##STR194##

¹ H - NMR in D₆ -DMSO (TMS as internal standard):

δ=1.20 (t, 3H), 3.27 (q, 2H), 3.58 (t, 2H), 4.19 (t, 2H), 4.68 (s, 2H),7.32 (dd, 1H), 7.46 (d, 1H), 7.60 (d, 1H), 9.10 (br, NH) ppm. ##STR195##

¹ H - NMR in D₆ -DMSO (TMS as internal standard):

δ=1.13 (t, 3H), 2.97 (m, 2H), 3.30 (t, 2H), 4.09 (t, 2H), 4.27 (S, 2H),6.08 (m, 1H), 6.45 (m, 2H), 6.98 (m, 1H) ppm. ##STR196##

¹ H - NMR in D₆ -DMSO (TMS as internal standard):

δ=1.20, (t, 3H), 2.41 (s, 3H), 3.38 (m, 2H), 3.58 (t, 2H), 4.20 (t, 2H),4.65 (s, 2H), 7.40 (m, 3H) ppm. ##STR197##

¹ H - NMR in D₆ -DMSO (TMS as internal standard):

δ=1.21 (t, 3H), 3.35 (q, 2H), 3.45 (t, 2H), 3.89 (s, 3H), 4.15 (t, 3H),4.56 (s, 3H), 7.23 (d, 1H), 7.52 (m, 2H) ppm.

The following compounds are obtained analogously, ##STR198##

EXAMPLE 76

78.4 g of 1-amino-8-hydroxynaphthalene-3,6-disulphonic acid (as themonosodium salt) are dissolved in 800 ml of water at a pH of 6.5. Aftercooling to 0° C., 21.5 ml of cyanuric fluoride is swiftly run in, andthe pH is maintained at 4.0 to 4.5 using 20% strength sodium carbonatesolution and the temperature is further maintained around 0° C.

72 g of the component of the formula ##STR199## are dissolved in 500 mlof water by addition of 55 ml of 10% strength lithium hydroxide solutionup to a pH of 6.9 at 0° to 3° C. The two solutions are combined, and thepH in the reaction mixture is maintained at 5.0 to 5.2 using 2N sodiumcarbonate solution.

51.3 g of 2-aminonaphthalene-1-sulphonic acid are dissolved in 575 ml ofwater by neutralisation using sodium hydroxide solution at a pH of 6.5and 0° C. 57.5 ml of concentrated hydrochloric acid are added in oneportion, and the mixture is then diazotised using 57.5 ml of 4N sodiumnitrile solution. Stirring is continued for one hour, and any excessnitrite is then destroyed using sulphamic acid solution.

The diazo suspension obtained is then poured into the solution preparedabove at 0° to 5° C., during which the pH in the mixture is maintainedat 7.0 using 2N sodium carbonate solution. After 3 hours, thetemperature is allowed to rise to 20° C., and stirring of the mixture iscontinued until the coupling is complete. The dyestuff obtained of theformula ##STR200## is salted out with sodium chloride, isolated and,after addition of a small amount of phosphate buffer, dried in vacuo at50° C.

This dyestuff dyes cotton from a long liquor at an optimum dyeingtemperature of 50° C. in bluish red hues giving high fixation yields.

λ_(max) =546 nm in water.

EXAMPLE 77

78.4 g of 1-amino-8-hydroxynaphthalene-3,6-disulphonic acid are reactedas in Example 76 with 21.5 ml of cyanuric fluoride. A solution of 89.5 gof the component of the formula ##STR201## obtained by the procedure ofExample 80, neutralised up to a pH of 6 and cooled to 0° to 3° C. isthen added over a period of a few minutes, and the pH is maintained at5.2 using 2N sodium carbonate solution.

When condensation is complete, a diazo suspension prepared from 51.3 gof 2-aminonaphthalene-1-sulphonic acid according to Example 76 is added.During this addition, the pH in the coupling mixture is maintained at7.0 to 7.5 using sodium carbonate solution. The temperature is allowedto rise gradually to 10° C. over a period of 21/2 hours and then to 20°C. overnight, during which the pH is further maintained at 7.0. Thedyestuff is salted out with potassium chloride, filtered off withsuction and washed with 25% strength potassium chloride solution. Afteraddition of phosphate buffer, it is dried in vacuo at 50° C.

It has the formula ##STR202## and dyes cotton in bluish red hues at anoptimum dyeing temperature of 50° C. and a high fixation yield.

λmax=546 nm in water.

EXAMPLE 78

78.4 g of 1-amino-8-hydroxynaphthalene-3,6-disulphonic acid arecondensed by the procedure of Example 1 with 21.5 ml of cyanuricfluoride.

A solution of 72 g of ##STR203## in 250 ml of water, cooled to 0° to 3°C. and brought to a pH of 5, is run in over a period of 10 minutes,during which the pH is maintained at 5.2 using 2N sodium carbonatesolution.

The solution is prepared by sulphation of 2-(x-aminophenylethyl)2-hydroxyethyl sulphone by the procedure of Example 81.

69.7 g of 2-aminonaphthalene-1,5-disulphonic acid are dissolved in 500ml of water by addition of sodium hydroxide solution up to a pH of 7.The solution is cooled to 0° C., 67.5 ml of 4N sodium nitrite solutionand 300 g of ice are added, and 60 ml of concentrated hydrochloric acidare poured in in one portion. After additional stirring for 1 hour,diazotisation is complete.

Sulphamic acid is added until no more nitrite can be detected.

The diazonium suspension is added at 0° C. to the initially introducedsolution of the coupling component prepared above, and the pH in thecoupling mixture is simultaneously maintained at 7.0 using dilute sodiumcarbonate solution. After 3 hours, the temperature is allowed to rise to20° C., and, after coupling is complete, the dyestuff is salted out. Itis filtered off with suction, washed and, after addition of a smallamount of phosphate buffer, dried. The dyestuff of the formula##STR204## dyes cotton from a long liquor at an optimum dyeingtemperature of 50° C. in bluish red hues giving good fixation hues.

λ_(max) =541 nm in water.

EXAMPLE 79

A. 500 g of styrene, 468 g of 2-mercaptoethanol, 5.0 g ofazoisobutyronitrile are stirred, during which the temperature rises to30° to 33° C. over a period of about one hour. Stirring overnight iscontinued, and the mixture is then heated at 50° C. for 5 to 6 hours.

The reaction is complete as soon as the ¹ H nuclear magnetic resonancespectrum no longer shows the characteristic styrene signals in the rangeof δ=4.80, 5.30 and 6.26 ppm.

The colourless liquid obtained has the formula ##STR205## and stillcontains small amounts of 2-mercaptoethanol. After dilution with 4.4 lof water, the mixture is oxidised directly to the sulphone (see SectionC).

B. The product obtained in A can also be obtained in the followingmanner:

176 g of 2-chloroethylbenzene, 107 g of 2-mercaptoethanol, 198 g ofpotassium carbonate and 840 ml of acetonitrile are refluxed at 86° C.for 4 hours with stirring and in a nitrogen atmosphere. The mixture ispoured into 8 l of water, extracted with methylene chloride, and themethylene chloride phase is extracted with 2N sodiumcarbonate solution,washed with water and dried over sodium sulphate. After the methylenechloride has been distilled off in a rotary evaporator, at the end invacuo at 50° C., a yellowish oil remains which is identical to the thioether of Section A and shows the same signals in the ¹ H-NMR spectrum.

¹ H-NMR (D₆ -DMSO)

δ=2.60 ppm (t, 2H)

δ=2.73-2.83 ppm (m, 4H)

δ=3.53-3.60 ppm (m, 2H)

δ=4.78 ppm (t, 1H)

δ=7.20-7.30 ppm (m, 5H)

C. 54 g of sodium acetate and 7 ml of glacial acetic acid are added tothe emulsion of the 2-hydroxyethyl 2-phenylethyl sulphide in 4.4 l ofwater obtained in Section 79A such that a pH of 5.2 is reached.

This is followed by addition of a solution of 7.9 g of tungstic acid in120 ml of water and 5 ml of 50% strength sodium hydroxide solution whichbefore addition was likewise brought to a pH of 5.2 with 7 ml of glacialacetic acid. 932 g of 35% strength hydrogen peroxide are then run in at55° to 60° C. over a period of one hour, during which a clear solutionis formed in between which towards the end of the addition becomescloudy again. A chromatographic sample shows that no more sulphide ispresent and substantially a mixture of the corresponding sulphoxide andsulphone is present. Oxidation to the sulphone is completed usinganother 480 g of 35% strength hydrogen peroxide and continuing to stirat 55° to 60° C. The mixture is then cooled to 0° C. The sulphone whichhas crystallised is filtered off with suction and washed with severalportions of ice-water. Drying gives 920 g of the product which melts at56° to 59° C.

¹ H-NMR (D₆ -DMSO)

δ=2.97-3.06 ppm (m, 2H)

δ=3.26 ppm (t, 2H)

δ=3.36-3.47 ppm (m, 2H)

δ=3.79-3.88 ppm (m, 2H)

δ=5.15 ppm (t, 1H)

δ=7.20-7.36 ppm (m, 5H)

D. 135 g of the above sulphone 79C are introduced at 0° C. into 445 mlof 96% strength sulphuric acid. As soon as a solution has been formed,120 g of a mixed acid consisting of 40 g of nitric acid and 80 g ofsulphuric acid are added dropwise at -20° C. over a period of 2 hours.The temperature is allowed to rise to room temperature overnight. Themixture obtained is poured into 1.5 kg of ice and 2.5 l of water, andthe resulting solution is refluxed at 106° C. for 4 hours in order tohydrolyse the sulphato group. The mixture is then cooled to 0° C. Uponstirring overnight or after seeding, the compound of the formula##STR206## crystallises from the emulsion.

Melting point: 92°-93° C.

¹ H-NMR (D₆ -DMSO)

δ=3.12-3.22 ppm (m, 2H)

δ=3.28 ppm (t, 2H)

δ=3.47-3.53 ppm (m, 2H)

δ=3.90 ppm (t, 2H)

δ=4.74 ppm (broad 1H)

δ=7.58 ppm (d, 2H)

δ=8.17 ppm (d, 2H)

E. 200 g of 2-(4-nitrophenyl)ethyl 2-hydroxyethyl sulphone from Example79D are catalytically reduced in 800 ml of methanol after addition of 10g of Raney nickel at 60° C. and a hydrogen pressure of 50 bar. Themixture is diluted with 1 l of methanol, the nickel is removed at theboil, and the filtrate is evaporated to dryness in a rotary evaporator,giving 172 g of an oil which upon cooling solidifies to a crystallinematerial: ##STR207##

Melting point: 58°-62° C.

¹ H-NMR (D₆ -DMSO)

δ=2.88-2.96 ppm (m, 2H)

δ=3.19-3.34 ppm (t,m, 4H)

δ=3.74-3.81 ppm (m, 2H)

δ=5.03 ppm (s, 2H)

δ=5.13 ppm (t, 1H)

δ=6.52 ppm (d, 2H)

δ=6.92 ppm (d, 2H)

F. 172 g of 2-(4-aminophenyl)ethyl 2-hydroxyethyl sulphone from Example79E are introduced at 0° C. into 260 ml of 96% strength sulphuric acid.85 ml of 20% strength oleum are then added dropwise at 0° C. over aperiod of 30 minutes with cooling, and stirring is continued for another21/2 hours with further cooling. The solution is poured onto 1.4 kg ofice-water, the resulting precipitate is filtered off with suction andwashed free of sulphuric acid with 1.5 l of isopropanol. Drying gives aproduct which has the formula ##STR208## and has a content of 97.6%,relative to this formula.

¹ H-NMR (D₆ -DMSO)

δ=3.00-3.08 ppm (m, 2H)

δ=3.34-3.48 ppm (m, 4H)

δ=4.17 ppm (t, 2H)

δ=7.28 ppm (d, 2H)

δ=7.48 ppm (d, 2H)

δ=approx. 9.7 ppm (broad)

EXAMPLE 80

100 g of 2-(aminophenyl)ethyl 2-hydroxyethyl sulphone are introducedinto a mixture of 147 ml of 20% strength oleum and 80 ml of 65% oleum at10° to 15° C. When everything is dissolved, another 80 ml of 65%strength oleum are added at 15° to 20° C. with cooling, and the mixtureis then stirred at 25° C. for 17 hours. A chromatographic sample aftersulphation also indicates complete sulphonation of the aromatic ring.The mixture is then poured onto 1.5 kg of ice at such a rate that thetemperature is maintained at 0° to 5° C. 460 g of calcium carbonate areadded at 0° to 5° C. to the solution obtained until a pH of 4.3 isreached. The calcium sulphate is filtered off with suction, washed withwater, and the combined filtrates are concentrated in vacuo at 35° C. ina rotary evaporator to about 500 g of solution. The solution of theproduct of the formula ##STR209## is obtained, whose content is found tobe 0.324 mol=99% of theory by titration with sodium nitrite solution inacid medium and which can be used directly for preparing the dyestuffsdescribed.

A sample of this solution completely evaporated in vacuo and dried showsthe following signals in the nuclear magnetic resonance spectrum:

¹ H-NMR (D₆ DMSO)

δ=3.28-3.48 ppm (m, 6H)

δ=4.13 ppm (t, 2H)

δ=6.75 ppm (d, 1H)

δ=7.20 ppm (d, 1H)

δ=7.32 ppm (s, 1H)

EXAMPLE 81

A. 135 g of the 2-hydroxyethyl 2-phenylethyl sulphone from Example 79Care introduced into 780 g of 90% strength sulphuric acid at 0° C. Themixture is then stirred at 25° C. for 30 minutes until a clear solutionis formed. 120 g of mixed acid consisting of 40 g of nitric acid and 80g of sulphuric acid are added dropwise at -13° to -7° C. over a periodof 4 to 5 hours, and the temperature is allowed to rise to about 0° C.overnight. The mixture is poured onto 2.7 kg of ice and 2 l of water andrefluxed at 106° to 107° C. for 4 hours. It is cooled to 0° C., thesomewhat soft crystalline material, after stirring overnight, isfiltered off with suction and washed acid-free with 1,500 ml of icewater. After drying in vacuo at room temperature, 133 g of a mixture ofisomers having a melting range of 69° to 83° C. and corresponding to theformulae ##STR210## is obtained, in which the p isomer is predominant.

B. 133 g of the mixture of nitro isomers obtained above are reduced in500 ml of methanol in an autoclave at 60° to 70° C. under a hydrogenpressure of 60 bar in the presence of Raney nickel. After clearing thesolution diluted with 400 ml of methanol at 64° C., the solutionobtained is evaporated. The remaining brownish oil crystallises uponstanding, giving 115 g of crystals having the formula ##STR211## and amelting range of 45° to 51° C.

C. For sulphation, 100 g of the above aminosulphone compound are meltedat 55° C., and the melt is slowly added dropwise to 150 ml of 96%strength sulphuric acid maintained at 25° C.

When everything is dissolved, the mixture is cooled to 0° C., 50 ml of20% strength oleum are added, and the mixture is stirred at 0° to 5° C.for 15 hours. The solution is poured onto 800 g of ice and 800 ml ofwater, neutralised up to a pH of 5.2 using about 338 g of calciumcarbonate, freed from calcium sulphate by filtration, the calciumsulphate is washed with water, and the combined filtrates areconcentrated to about 600 ml, giving a solution of the sulphato compoundof the formula ##STR212##

EXAMPLE 82

117 g of β-(4-nitrophenyl)ethyl chloride are heated to 50° to 60° C. in500 ml of ethanol together with 67 g of 2-mercaptoethanol and 124 g ofpotassium carbonate. After the reaction is complete, the ethanol isdistilled off in vacuo, the remaining oil is washed with water and,after emulsification in 400 ml of water, oxidised to the sulphone by theprocedure of Example 79C using hydrogen peroxide ##STR213##

EXAMPLE 83

Analogously to Example 82, exchange of the chlorine atom in2-nitrophenylethanol (after reaction with SOCl₂) for the2-mercaptoethanol radical and oxidation of the thio ether obtained withH₂ O₂ gives the compound of the formula ##STR214## from which, aftercatalytic reduction of the nitro group, followed by esterification usingsulphuric acid, the following compound can be prepared ##STR215##

EXAMPLE 84

Analogously to Example 79A, 49.7 g of 3-nitrostyrene, 31.5 g of2-mercaptoethanol and 0.4 g of azoisobutyronitrile are combined, themixture is stirred overnight and then heated to 50° C. The compoundobtained of the formula ##STR216## is oxidised analogously to Example79C to the sulphone using H₂ O₂, the nitro group is catalyticallyreduced, and the amino compound obtained is converted to the sulphatocompound of the formula ##STR217## using sulphuric acid.

EXAMPLE 85

Using the procedure of Example 76, a solution of the coupling component##STR218## is prepared from 78.4 g of1-amino-8-hydroxynaphthalene-3,6-disulphonic acid, 21.5 ml of cyanuricfluoride and 72 g of 2-(4-aminophenyl)ethyl 2-sulphatoethyl sulphone.

39.8 g of 2-aminobenzenesulphonic acid are dissolved in 300 ml of waterand 112 ml of 2N sodium hydroxide solution at a pH of 6. 57.5 ml of 4Nsodium nitrite solution are added. The solution obtained is run into apreviously prepared mixture of 200 ml of water, 60 ml of concentratedhydrochloric acid and 2.5 ml of 4N sodium nitrite solution at 0° to 2°C. over a period of 30 minutes.

Stirring is then continued for 1 hour, any excess nitrous acid isremoved using sulphamic acid, and the diazo suspension obtained isintroduced at 0° to 3° C. into the above solution of the couplingcomponent, during which the pH in the resulting mixture is maintained at6.5 by simultaneous addition of 2N sodium carbonate solution. Afterstirring for 2 hours with cooling, the temperature is allowed to rise to20° C.

After coupling is complete, the dyestuff is salted out with sodiumchloride, filtered off with suction, washed with 25% strength sodiumchloride solution and, after buffering, dried at 50° C. in vacuo.

It has the formula ##STR219## and dyes cotton from a long liquor at anoptimum dyeing temperature of 50° C. in red hues and in good fixationyields.

λ_(max) =532 nm in water.

Further dyestuffs are synthesised analogously from the components shownin the list below.

             No. Diazo component 1-Amino-8-hydroxy-naphthalene-disulph.     Triahalogeno-triazine      ##STR220##      Hue λ.sub.max (H.sub.2      O)                                                 86      ##STR221##      ##STR222##      ##STR223##      ##STR224##      bluish red 541 nm      87     ##STR225##      ##STR226##      ##STR227##      ##STR228##      bluish red 546 nm      88     ##STR229##      ##STR230##      ##STR231##      ##STR232##      bluish red 546 nm      89     ##STR233##      ##STR234##      ##STR235##      ##STR236##      red 532 nm      90     ##STR237##      ##STR238##      ##STR239##      ##STR240##      red 533 nm      91     ##STR241##      ##STR242##      ##STR243##      ##STR244##      bluish red      92     ##STR245##      ##STR246##      ##STR247##      ##STR248##      bluish red      93     ##STR249##      ##STR250##      ##STR251##      ##STR252##      bluish red      94     ##STR253##      ##STR254##      ##STR255##      ##STR256##      bluish red      95     ##STR257##      ##STR258##      ##STR259##      ##STR260##      bluish red 541 nm      96     ##STR261##      ##STR262##      ##STR263##      ##STR264##      bluish red 541 nm      97     ##STR265##      ##STR266##      ##STR267##      ##STR268##      bluish red      98     ##STR269##      ##STR270##      ##STR271##      ##STR272##      bluish red      99     ##STR273##      ##STR274##      ##STR275##      ##STR276##      bluish red  100      ##STR277##      ##STR278##      ##STR279##      ##STR280##      red  101      ##STR281##      ##STR282##      ##STR283##      ##STR284##      red  102      ##STR285##      ##STR286##      ##STR287##      ##STR288##      bluish red 545 nm

EXAMPLE 103

41.7 g of the azo compound of the formula ##STR289## are dissolved in800 ml of water by bringing the pH to 4.5 using 2N sodium hydroxidesolution. After cooling of the solution to 0° C., 8.2 ml of cyanuricfluoride are added dropwise over a period of 10 minutes, and the pH ismaintained at 4.5 to 4.7 using 2N sodium carbonate solution. Stirring iscontinued for 10 minutes, and a neutral solution of 39.4 g of thecomponent of the formula ##STR290## in 150 ml of water, which isobtained by the procedure of Example 80, is then added. While thissolution is metered in, the temperature is further maintained at 0° to2° C. and the pH at 5.5 to 5.7 with sodium carbonate solution. After 2hours, the temperature is allowed to rise to 20° C. When condensation iscomplete, the dyestuff is salted out with potassium chloride, filteredoff with suction, washed with 15% strength potassium chloride solutionand, after addition of a small amount of phosphate buffer solution,dried at 50° C. in vacuo.

The dyestuff of the formula ##STR291## dyes cotton from a long liquor atan optimum dyeing temperature of 50° C. and a high fixation yield inscarlet hues.

λ_(max) =500 nm in water.

EXAMPLE 104

24.5 g of the azo compound of the formula ##STR292## are dissolved in340 ml of water at a pH of 7. After cooling to 0° to 2° C., the pH isbrought to 4.5 using dilute hydrochloric acid, and 4.3 ml of cyanuricfluoride are immediately added dropwise over a period of 4 minutes. ThepH is further maintained at 4.5 with 2N sodium carbonate solution. 15minutes later, the reaction is complete. A solution of 18.6 g of thecomponent of the formula ##STR293## in 100 ml of water, which wasbrought to a pH of 6 with 10% strength lithium hydroxide solution, isadded, and the pH in the reaction mixture is maintained at 5.0 to 5.5.After 2 hours, the temperature is allowed to rise to 20° C. 1 g ofprimary sodium phosphate is added, the pH is brought to 5.5 with sodiumhydroxide solution, and the solution is then evaporated at 35° to 40° C.in vacuo in a rotary evaporator, giving an orange powder which dyescotton from a long liquor at an optimum dyeing temperature of 40° to 60°C. and excellent fixation yield in reddish orange hues.

The dyestuff obtained has the formula ##STR294##

Further orange-dyeing dyestuffs are obtained by condensing the followingazo components analogously with cyanuric fluoride and aminophenylalkylβ-sulphatoethyl sulphones.

           No. Azo component      ##STR295##      Hue λ.sub.max (H.sub.2      O)                                               105      ##STR296##      ##STR297##      orange 486 nm      106     ##STR298##      ##STR299##      orange 485 nm      107     ##STR300##      ##STR301##      orange      108     ##STR302##      ##STR303##      orange 483 nm      109     ##STR304##      ##STR305##      orange 482 nm      110     ##STR306##      ##STR307##      orange      111     ##STR308##      ##STR309##      orange      112     ##STR310##      ##STR311##      scarlet      113     ##STR312##      ##STR313##      scarlet 502 nm      114     ##STR314##      ##STR315##      orange      115     ##STR316##      ##STR317##      orange 486 nm      116     ##STR318##      ##STR319##      yellowish red      117     ##STR320##      ##STR321##      yellowish red      118     ##STR322##      ##STR323##      yellowish red 501 nm      119     ##STR324##      ##STR325##      scarlet 501 nm      120     ##STR326##      ##STR327##       501 nm

EXAMPLE 12

35.0 g of the coupling product of 2-aminonaphthalene-6,8-disulphonicacid with 3-aminoacetanilide are dissolved in 600 ml of water at a pH of5.5 with heating to 50° C. The mixture is cooled to 0° C., and 7.7 ml ofcyanuric fluoride are added dropwise over a period of 5 to 10 minutes.During this addition, the pH is maintained at 5.2 to 5.5 using dilutesodium carbonate solution. When the reaction is complete after about 10to 15 minutes, a solution of 35.0 g of the compound ##STR328## in 120 mlof water, brought to a pH of 5.5, is added dropwise, and the pH ismaintained at 5.5 to 5.7 with dilute sodium carbonate solution and thetemperature at 0° to 5° C., later increasing to 15° to 20° C. Afteraddition of 1.5 g of phosphate buffer of pH 6, the solution obtained isevaporated at 35° to 40° C. in vacuo or spray-dried. The dyestuffobtained of the formula ##STR329## dyes cotton from a long liquor at anoptimum dyeing temperature of 50° C. in golden yellow hues.

λ_(max) =389 nm in water.

Further reddish yellow-dyeing dyestuffs are obtained by condensation ofthe following p-aminoazo compounds with cyanuric fluoride andaminophenylalkyl β-sulphatoethyl sulphones.

            No. Azo component Trihalogenotriazine      ##STR330##      Hue λ.sub.max (H.sub.2      O)                                                122      ##STR331##      ##STR332##      ##STR333##      reddish yellow 416 nm      123     ##STR334##      ##STR335##      ##STR336##      reddish yellow 393 nm      124     ##STR337##      ##STR338##      ##STR339##      reddish yellow 389 nm      125     ##STR340##      ##STR341##      ##STR342##      reddish yellow      126     ##STR343##      ##STR344##      ##STR345##      reddish yellow      127     ##STR346##      ##STR347##      ##STR348##      reddish yellow      128     ##STR349##      ##STR350##      ##STR351##      reddish yellow 386 nm      129     ##STR352##      ##STR353##      ##STR354##      reddish yellow      130     ##STR355##      ##STR356##      ##STR357##      reddish yellow 386 nm      131     ##STR358##      ##STR359##      ##STR360##      reddish yellow      132     ##STR361##      ##STR362##      ##STR363##      orange

EXAMPLE 133

24.2 g of the aminoazopyrazolone of the formula ##STR364## (prepared bycoupling diazotised 2-amino-4-formylaminobenzenesulphonic acid onto1-(4'-sulphophenyl)-3-carboxy-5-pyrazolone and hydrolysis using dilutesodium hydroxide solution) are dissolved in the form of the sodium saltin 600 ml of water. The solution is cooled to 0° to 2° C., the pH isbrought to 5.0 with dilute hydrochloric acid, and 4.0 ml of cyanuricfluoride are added dropwise immediately over a period of about 5minutes. During this addition, the pH is continuously maintained between4.3 and 4.6 using 2N sodium carbonate solution. When the reaction iscomplete after 15 minutes, a solution of 17.0 g of the compound of theformula ##STR365## in 120 ml of water, brought to a pH of 5.7 withlithium hydroxide solution, is added at 0° to 5° C. During thisaddition, the pH is maintained at 5.5 to 6 with 2N sodium carbonatesolution, and the temperature is allowed to rise to 20° C. after 2hours.

The dyestuff obtained of the formula ##STR366## dyes cotton from a longliquor in greenish yellow hues in a high fixation yield.

EXAMPLE 134

If the 5-amino-2-sulphophenylazopyrazolone component in Example 133 isreplaced by an equivalent amount of the corresponding4-amino-2-sulphophenylazopyrazolone, a dyestuff of the formula##STR367## is obtained which dyes cotton in reddish yellow hues like theone from Example 133.

Further yellow dyestuffs having similar properties are obtained bycondensing the following aminophenylazopyrazolones with cyanuricfluoride and the aminophenylalkyl β-sulphatoethyl sulphones listed.

    __________________________________________________________________________     No.                                                                              Aminophenylazopyrazolone                                                                                  ##STR368##                                    __________________________________________________________________________    135                                                                               ##STR369##                                                                                                ##STR370##                                    136                                                                               ##STR371##                                                                                                ##STR372##                                    137                                                                               ##STR373##                                                                                                ##STR374##                                    138                                                                               ##STR375##                                                                                                ##STR376##                                    139                                                                               ##STR377##                                                                                                ##STR378##                                    140                                                                               ##STR379##                                                                                                ##STR380##                                    141                                                                               ##STR381##                                                                                                ##STR382##                                    __________________________________________________________________________

EXAMPLE 142

19.9 g of the azo compound of the formula ##STR383## prepared bycoupling diazotised 4-acetylamino-2-aminobenzenesulphonic acid onto1,4-dimethyl-6-hydroxy-5-aminocarbonyl-3-sulphomethyl-2-pyridone andhydrolysis of the acetylamino group in dilute sodium hydroxide solutionare dissolved in 400 ml of water at a pH of 5.0. After cooling to 0° C.,4.1 ml of cyanuric fluoride are run in, and the pH is maintained at 4.5with 2N sodium carbonate solution. Stirring under the same conditions iscontinued for another 15 minutes, and a solution of 15.7 g of thecomponent of the formula ##STR384## in 110 ml of water, neutralised withlithium hydroxide, is then added. The pH is maintained at 5.5 to 5.7with sodium carbonate solution, the temperature continuously? at 0° to3° C., and the condensation is brought to completion by stirringovernight. The dyestuff is salted out with potassium chloride, filteredoff with suction and washed with 15% strength potassium chloridesolution.

It has the formula ##STR385## and dyes cotton from a long liquor at anoptimum dyeing temperature of 40° to 50° C. in brilliant greenish yellowshades.

Similar dyestuffs are obtained by reacting the components of Examples143 to 154 with one another by the procedure of Example 142.

            No. Azo component Trihalogenotriazine      ##STR386##      Hue λ.sub.max (H.sub.2      O)                                                143      ##STR387##      ##STR388##      ##STR389##       greenish yellow 423 nm      144     ##STR390##      ##STR391##      ##STR392##      greenish yellow      145     ##STR393##      ##STR394##      ##STR395##      yellow      146     ##STR396##      ##STR397##      ##STR398##      yellow      147     ##STR399##      ##STR400##      ##STR401##      greenish yellow      148     ##STR402##      ##STR403##      ##STR404##      greenish yellow 422 nm      149     ##STR405##      ##STR406##      ##STR407##      greenish yellow 421 nm      150     ##STR408##      ##STR409##      ##STR410##      greenish yellow 421 nm      151     ##STR411##      ##STR412##      ##STR413##      greenish yellow      152     ##STR414##      ##STR415##      ##STR416##      greenish yellow      153     ##STR417##      ##STR418##      ##STR419##      greenish yellow 421 nm      154     ##STR420##      ##STR421##      ##STR422##      yellow

EXAMPLE 155

2 g of sodium fluoride are added to a solution of 22.6 g of thecomponent of the formula ##STR423## in 60 ml of water, obtained by theprocedure of Example 80, and the mixture is brought to a pH of 3.5. 5.2ml of cyanuric fluoride are added dropwise at 0° C. over a period of 5minutes, and the pH is maintained at 3.5 to 3.7 using about 54 ml of 2Nsodium carbonate solution.

25 g of1-amino-4-(2'-aminomethyl-4'-methyl-6'-sulphophenylamino)anthraquinone-2-sulphonicacid are dissolved in 400 ml of water and 50 ml of acetone byneutralisation with about 28 ml of 2N sodium hydroxide solution at a pHof 7. After cooling of the solution to 0° to 5° C., the solution of theabove reactive component is run in, and the pH is maintained at 6.5 with2N sodium carbonate solution. After condensation is complete, thedyestuff is either salted out or isolated by evaporation in vacuo at 35°to 40° C. It has the formula ##STR424## can be used for the printing ordyeing of cellulose fabric by continuous processes and produces clearreddish blue shades. At the same time, very high fixation yields areobtained (λ_(max) =624 and 587 nm in H₂ O).

EXAMPLE 156

14.7 g of 1-amino-4-(3'-aminophenylamino)anthraquinone-2,4'-disulphonicacid are dissolved in 250 ml of water at a pH of 5 and 0° to 5° C. 2.8ml of cyanuric fluoride are added dropwise to the solution of thedyestuff component over a period of 5 to 10 minutes, and the pH ismaintained at 4.2 to 4.7 with 2N sodium carbonate solution. After ashort period of additional stirring, the condensation to give thedifluorotriazinyl dyestuff is complete.

A neutralised solution of 12.3 g of the compound of the formula##STR425## in 40 ml of water is then slowly added to the solution of thereactive dyestuff component, and the pH is maintained at 5.0 to 5.6.After the addition, the pH is maintained at 6.0 to 6.5, and thetemperature is allowed to rise gradually to 20° C. over a period of 15hours, after which condensation is complete. The dyestuff solution isthen salted out over a period of 2 hours. The precipitated dyestuff ofthe formula ##STR426## is filtered off with suction and washed with saltsolution until the runoff is clear. Drying in vacuo at 45° C. gives aproduct which can be used to dye and print cellulose fabric in blue huesand high fixation yields.

EXAMPLE 157

16.7 g of the component of the formula ##STR427## are dissolved in 80 mlof water, and the solution is brought to a pH of 4.0. 1.9 g of sodiumfluoride are added to the solution, which is cooled to 0° to 2° C. 4.2ml of cyanuric fluoride are then run in with further cooling, and the pHis maintained between 4.0 and 4.2 with sodium carbonate solution. About15 minutes after the addition of cyanuric fluoride, the reaction hasgone entirely to completion. The solution is then brought to a pH of 4.5to 5.0. A neutralised solution of 19.0 g of1-amino-4-(3'-amino-2'-methylphenylamino)-anthraquinone-2,5'-disulphonicacid in 350 ml of water is added dropwise over a period of 30 mintues tothe reactive component obtained. During this addition, the temperaturein the reaction solution is further maintained at 0° to 5° C. and the pHat 6.0 to 6.5 using sodium carbonate solution. After 2 hours, thetemperature is allowed to increase gradually to 10° C. over a period of15 hours. After condensation is complete, the dyestuff of the formula##STR428## is salted out from the solution using sodium chloride,filtered off with suction, washed with 20% strength sodium chloridesolution and dried in vacuo at 45° C.

The dyestuff produces on cotton blue dyeings and prints in a highfixation yield.

Further blue anthraquinone dyestuffs having similar properties areobtained by condensing the anthraquinone components listed below of thegeneral formula ##STR429## with the trihalogenotriazines and thesulphatoethylsulphonylalkylanilines by one of the methods describedabove.

    __________________________________________________________________________     No.                                                                              ##STR430##      Trihalogenotriazine                                                                     ##STR431##           Hue    λ.sub.max                                                              (H.sub.2            __________________________________________________________________________                                                             O)                   158                                                                               ##STR432##                                                                                    ##STR433##                                                                              ##STR434##          blue   598 nm               159                                                                               ##STR435##                                                                                    ##STR436##                                                                              ##STR437##          blue   597 nm               160                                                                               ##STR438##                                                                                    ##STR439##                                                                              ##STR440##          reddish blue                161                                                                               ##STR441##                                                                                    ##STR442##                                                                              ##STR443##          blue                        162                                                                               ##STR444##                                                                                    ##STR445##                                                                              ##STR446##          greenish blue               163                                                                               ##STR447##                                                                                    ##STR448##                                                                              ##STR449##          reddish                                                                              624 nm               164                                                                               ##STR450##                                                                                    ##STR451##                                                                              ##STR452##          reddish blue                165                                                                               ##STR453##                                                                                    ##STR454##                                                                              ##STR455##          clear                                                                                635 nm               166                                                                               ##STR456##                                                                                    ##STR457##                                                                              ##STR458##          clear                       __________________________________________________________________________                                                      blue                    

EXAMPLE 167

65 g of the sodium salt of the compound of the formula ##STR459## aredissolved in 200 ml of water at a pH of 7.5. The solution is cooled to0° C., and 9 g of trifluorotriazine are added dropwise over a period of20 minutes, during which the pH is maintained at 6 to 7 by addition ofsodium carbonate solution. After the reaction is complete, a neutralisedsolution of 18.3 g of the compound of the formula ##STR460## in 80 ml ofwater, prepared by the procedure of Example 6, is added dropwise, andthe pH is maintained at 7 with sodium carbonate solution. Aftercondensation is complete, the dyestuff is isolated either by evaporationor spray-drying or by salting-out. The dyestuff thus obtained of theformula ##STR461## dyes cotton in blue hues having good fastnessproperties.

EXAMPLE 168

A further valuable dyestuff is obtained by repeating the procedure ofExample 167, using the sodium salt of the compound of the formula##STR462## instead of the dyestuff base used there. The dyestuff thusobtained of the formula ##STR463## dyes cotton in blue hues having goodfastness properties.

EXAMPLE 169

If in Example 91 equivalent amounts of 2-(2-aminophenyl) 2-sulphatoethylsulphone are used instead of the mixture of isomers2-(x-aminophenyl)ethyl 2-sulphatoethyl sulphone used there, the dyestuffof the formula ##STR464## is obtained, which dyes cotton in blue hues bythe application methods customary for reactive dyestuffs.

Further formazan dyestuffs in the table below are obtained by combiningthe corresponding components.

                                      TABLE 1                                     __________________________________________________________________________     ##STR465##                                                                   Ex.                                                                              R.sub.1                                                                           R.sub.2                                                                           Hal                                                                              A                        Hue                                    __________________________________________________________________________    170                                                                              SO.sub.3 H                                                                        H   F                                                                                 ##STR466##              blue                                   171                                                                              SO.sub.3 H                                                                        H   F                                                                                 ##STR467##              blue                                   172                                                                              SO.sub.3 H                                                                        H   F                                                                                 ##STR468##              blue                                   173                                                                              H   SO.sub.3 H                                                                        F                                                                                 ##STR469##              blue                                   174                                                                              H   SO.sub.3 H                                                                        F                                                                                 ##STR470##              blue                                   175                                                                              H   SO.sub.3 H                                                                        Cl                                                                                ##STR471##              blue                                   __________________________________________________________________________

EXAMPLES 176 TO 183

Further dyestuffs according to the invention of the general formula##STR472## can be prepared analogously to the exemplary embodiment byreacting the components listed in Table 2.

The dyestuffs obtained have very good fibre-reactive dyestuff propertiesand produce, by the customary dyeing and printing processes, dyeings andprints of high colour strength and good fastness properties in the hueon cotton listed in the particular table examples.

      Ex. R.sub.1 R.sub.2 R.sub.3 R.sub.4 R.sub.5 A Hue               176 SO.sub.3 H H SO.sub.3      H     ##STR473##      SO.sub.3      H     ##STR474##      reddish blue  177 SO.sub.3      H H H     ##STR475##      SO.sub.3      H     ##STR476##      blue  178 H SO.sub.3 H SO.sub.3      H     ##STR477##      SO.sub.3      H     ##STR478##      reddish blue  179 H SO.sub.3      H H     ##STR479##      SO.sub.3      H     ##STR480##      blue      180 H     ##STR481##      SO.sub.3 H SO.sub.3 H SO.sub.3      H     ##STR482##      blue      181     ##STR483##      H SO.sub.3 H SO.sub.3 H SO.sub.3      H     ##STR484##      reddish  182 H SO.sub.3 H SO.sub.3 H SO.sub.3      H     ##STR485##      ##STR486##      reddish blue  182 H SO.sub.3      H     ##STR487##      SO.sub.3      H H     ##STR488##      greenish blue

EXAMPLE 184

A neutralised solution of 14.4 g of the component of the formula##STR489## and 1.6 g of sodium fluoride in 60 ml of water is cooled to0° to 2° C. 5.5 g of cyanuric fluoride are run in, and the pH ismaintained between 3.5 and 4.0 using 2N sodium carbonate solution. Aftercondensation is complete, the pH is brought to 5.0.

32 g of the copper phthalocyanine component of the formula ##STR490##prepared by the procedure given in European Patent 0,073,267 aredissolved in 300 ml of water at a pH of 7.0 to 7.5. The solution of theabove condensation product is then run into the dye component at 0° to5° C., and the pH in the reaction mixture is maintained at 7.0 to 7.5.After 3 hours, the temperature is allowed to rise gradually to 20° C.,and the pH is further kept constant. After the reaction is complete, theproduct obtained is salted out from the solution, filtered off withsuction, buffered with a small amount of phosphate solution of pH 6.0and dried in vacuo at 45° C. The dyestuff has the formula ##STR491##

The dyestuff produces light greenish blue dyeings and prints oncellulose fibres.

EXAMPLE 185

Example 184 is repeated, using 32.4 g of the copper phthalocyaninecompound of the formula ##STR492## (prepared by condensation of copperphthalocyanine tetra(sulpho chloride/sulphonic acid) withmonoacetylethylenediamine, followed by hydrolysis according to theprocedure given in German Offenlegungsschrift 1,644,681, Example 2)instead of the 32 g of the copper phthalocyanine component used there,giving a dyestuff of the formula ##STR493## which produces lightgreenish blue dyeings and prints on cellulose fabric in high yield.

λ_(max) =668 nm, 628 nm in H₂ O.

EXAMPLE 186

31.2 g of the copper phthalocyanine compound of the formula ##STR494##prepared by condensation of copper phthalocyanine tetra-(sulphochloride/sulphonic acid) with 3-aminoacetanilide and ammonia, followedby hydrolysis of the acetylamino group in dilute sodium hyroxidesolution at 75° C. are dissolved in 420 ml of water at a pH of 7. 3.1 mlof cyanuric fluoride are added dropwise to the solution at 0°-3° C., andthe pH is maintained at 4.5 to 5.0 with 2N sodium carbonate solution.After condensation is complete, a solution of 11.5 g of the reactivecomponent of Example 6C in 50 ml of water is added, and condensationwith the difluorotriazinyl dyestuff is completed at a pH of 5.5 to 6first at 0° to 5° C. and later increasing towards room temperature. Thedyestuff obtained of the formula ##STR495## is isolated by evaporationin vacuo or spray-drying or by salting-out, the mixture being bufferedto a pH of 6 before the drying process with a small amount of phosphate.The dyestuff dyes and prints cotton by the processes known for reactivedyestuffs in light greenish blue hues of good fastness properties and inhigh yield.

Further phthalocyanine reactive dyestuffs are obtained by condensing thephthalocyanine components shown in the list below, trifluorotriazine andβ-sulphatoethylsulphonylalkylaniline with one another by one of themethods described above.

    __________________________________________________________________________    Sulphatoethylsulphonyl-    β                                             No.                                                                              Phthalocyanine component                                                                              alkylaniline         Hue     λ.sub.max                                                              (H.sub.2 O)           __________________________________________________________________________    187                                                                               ##STR496##                                                                                            ##STR497##          greenish                                                                              668, 628 nm           188                                                                               ##STR498##                                                                                            ##STR499##          greenish blue                 189                                                                               ##STR500##                                                                                            ##STR501##          bluish green                  190                                                                               ##STR502##                                                                                            ##STR503##          bluish green                  191                                                                               ##STR504##                                                                                            ##STR505##          bluish green grun             192                                                                               ##STR506##                                                                                            ##STR507##          greenish blue                 193                                                                               ##STR508##                                                                                            ##STR509##          greenish blue                 194                                                                               ##STR510##                                                                                            ##STR511##          greenish blue                 195                                                                               ##STR512##                                                                                            ##STR513##          greenish blue                 196                                                                               ##STR514##                                                                                            ##STR515##          greenish blue                 197                                                                               ##STR516##                                                                                            ##STR517##          greenish blue                 198                                                                               ##STR518##                                                                                            ##STR519##          greenish                                                                              668, 627 nm           199                                                                               ##STR520##                                                                                            ##STR521##          greenish                                                                              668, 627              __________________________________________________________________________                                                            nm                

EXAMPLE 200

36.7 g of the aminodisazo compound of the formula ##STR522## prepared inthe known manner are dissolved in 400 ml of water at a pH of 6.0. Aftercooling of the solution to 0° C., 5.0 ml of cyanuric fluoride areswiftly added dropwise, and the pH is maintained at 4.5 to 5.0 with 2Nsodium carbonate solution.

After this first condensation step is complete, 17.4 g of the mixture ofisomers from Example 81C are introduced, and the pH is maintained at 5.5to 6.0 with sodium carbonate solution. Stirring at 0° to 5° C. iscontinued for 2 hours, and the temperature is then allowed to rise to20° C. with further pH control. The dyestuff obtained of the formula##STR523## is salted out with sodium chloride, filtered off with suctionand, after buffering at a pH of 6, dried in vacuo at 45° C. It dyescotton by the processes known for reactive dyestuffs in brown hues andhigh yield.

EXAMPLE 201

If the compound of the formula ##STR524## is used instead of theaminodisazo compound of Example 200 and condensed with cyanuric fluorideand then with a compound of the formula ##STR525## a dyestuff of theformula ##STR526## is obtained which likewise dyes cotton in brown huesand high yield.

Further brown reactive dyestuffs are obtained by condensation of thefollowing components.

        Trihalogeno- β     Sulphatoethylsulphonyl-  No. Aminodisazo compound triazine alkylaniline     Hue            202      ##STR527##      ##STR528##      ##STR529##      brown      203     ##STR530##      ##STR531##      ##STR532##      brown      204     ##STR533##      ##STR534##      ##STR535##      brown      205     ##STR536##      ##STR537##      ##STR538##      orange-brown

EXAMPLE 206

50.3 g of the aminoazo compound of the formula ##STR539## are dissolvedin 400 ml of water at a pH of 6. The solution is cooled to 0° to 2° C.,and 9.3 ml of cyanuric fluoride are added dropwise over a period of afew minutes. During this operation, the pH is maintained at 4.5 with 2Nsodium carbonate solution and stirring of the mixture is then continuedunder the same conditions for a short period. When the consumption ofsodium carbonate has come to a standstill, a solution of 32.3 g of4-[(2-sulphatoethylsulphonyl)ethyl]aniline in 180 ml of water, broughtto a pH of 6 with 10% strength lithium hydroxide solution, is run in,and the pH in the reaction mixture is maintained at 5.5 to 6.0. After 3hours, the temperature is allowed to rise gradually to 20° C., and thedyestuff obtained of the formula ##STR540## is isolated by salting outand filtering off with suction. Gentle drying gives a powder which dyescotton by the customary methods in scarlet hues and high yield.

EXAMPLE 207

If the aminoazo compound in Example 206 is replaced by an equivalentamount of the isomeric compound ##STR541## and this compound iscondensed with cyanuric fluoride and in a second step with a compound ofthe formula ##STR542## the dyestuff of the formula ##STR543## isobtained which dyes cotton in reddish orange hues and high fixationyields.

Further reactive dyestuffs based on aminoazonaphthol compounds areobtained by condensation of the components below.

        Trihalogeno- β     Sulphatoethylsulphonyl-  No. Aminoazonaphthol component triazine     alkylaniline Hue            208      ##STR544##      ##STR545##      ##STR546##      orange      209     ##STR547##      ##STR548##      ##STR549##      orange      210     ##STR550##      ##STR551##      ##STR552##      yellowish red      211     ##STR553##      ##STR554##      ##STR555##      orange      212     ##STR556##      ##STR557##      ##STR558##      brown      213     ##STR559##      ##STR560##      ##STR561##      brown

EXAMPLE 214

According to Example 184, 19.5 g of the component of the formula##STR562## are condensed with 7.4 g of cyanuric fluoride in 80 ml ofwater in the presence of 2.1 g of sodium fluoride. The solution obtainedof the condensation product is run into a solution of 31 g of the azocompound of the formula ##STR563## in 300 ml of water, brought to a pHof 7 and cooled to 0° to 5° C., and the pH in the mixture is maintainedat 6.5 with dilute sodium carbonate solution. After 3 hours, thetemperature is gradually increased to 20° C. After condensation iscomplete, the dyestuff is isolated by salting it out and filtering itoff with suction and, after buffering to a pH of 6.5, drying it in vacuoat 45° C. It has the formula ##STR564## and dyes cotton from a longliquor in bluish red hues and high fixation yields.

Similar red dyestuffs are obtained by reaction of the followingcomponents.

    __________________________________________________________________________                                     Trihalogeno-                                 No.                                                                              Azo component                 triazine  2-Sulphatoethylsulphonylalkylan                                               iline                              __________________________________________________________________________    215                                                                               ##STR565##                                                                                                  ##STR566##                                                                              ##STR567##                        216                                                                               ##STR568##                                                                                                  ##STR569##                                                                              ##STR570##                        217                                                                               ##STR571##                                                                                                  ##STR572##                                                                              ##STR573##                        218                                                                               ##STR574##                                                                                                  ##STR575##                                                                              ##STR576##                        __________________________________________________________________________

EXAMPLE 219

According to Example 184, 19.5 g of the component from Example 80 in 80ml of water and 2.1 g of sodium fluoride are condensed with 7.5 g ofcyanuric fluoride.

22.1 g of the triphendioxazine compound of the formula ##STR577## aredissolved in 300 ml of water at a pH of 11.5-12 by addition of sodiumhydroxide solution.

This solution and the reactive components prepared above are addeddropwise simultaneously to 80 ml of initially introduced ice water, andthe pH in the reaction mixture is maintained at 8-8.5 using 2N sodiumhydroxide solution and the temperature is further maintained at 0°-2° C.After several hours, the reaction is complete. The temperature isallowed to rise to 20° C. overnight. The dyestuff is salted out,filtered off with suction and, after buffering to a pH of 6.7, dried at45° C. in vacuo. It has the formula ##STR578## and dyes cotton by thecustomary methods in strong blue hues and high fixation yields.

EXAMPLE 220

27 g of the triphendioxazine compound of the formula ##STR579## aredissolved in 1,000 ml of water by bringing the pH to 7.0 with 10%strength lithium hydroxide. The solution is cooled to 0° to 5° C., and5.3 ml of cyanuric fluoride are added dropwise. The pH in the reactionmixture is maintained at 6.0 to 6.5 by dropwise addition of 10% lithiumhydroxide solution. To complete the reaction, the temperature is raisedto 20° C. over a period of 2 hours, and the pH is further maintainedwithin the above limits until the consumption of neutralising agent hascome to a standstill. A neutralised solution of 18.5 g of the componentfrom Example 81C in 80 ml of water is then added to the primarycondensation product, and the pH is further maintained at 6.0 to 6.5with lithium hydroxide.

The dyestuff obtained of the formula ##STR580## dyes cotton from a longliquor at an optimum dyeing temperature of 70° to 80° C. in strongreddish blue shades.

Further triphendioxazine reactive dyestuffs are prepared by a procedureanalogous to that from Examples 219 and 220 by condensation of thefollowing components:

      No. Triphendioxazine Trihalogenotriazine β     Sulphatoethylsulphonylalkylaniline Hue            221      ##STR581##      ##STR582##      ##STR583##      blue      222     ##STR584##      ##STR585##      ##STR586##      blue      223     ##STR587##      ##STR588##      ##STR589##      blue      224     ##STR590##      ##STR591##      ##STR592##      bluish red      225     ##STR593##      ##STR594##      ##STR595##      reddish blue

EXAMPLE 226

35.2 g of the known compound ##STR596## are dissolved in 350 ml ofwater, and the pH of the solution is brought to 5.0. The solution iscooled to 0° C., 7.4 g of cyanuric fluoride are added dropwise, and thepH is maintained at 4.5 with 2N sodium carbonate solution. After thereaction is complete, a neutralised solution of 17.0 g of the componentfrom Example 79F in 70 ml of water is added, and the pH is maintained at6.0 with 2N sodium carbonate solution, the temperature first beingmaintained at 0° to 5° C. for 4 hours and then being gradually increasedto 20° C. After conclusion of the condensation, the dyestuff, afterbuffering to a pH of 6, is isolated either directly by spray-drying orby salting-out, filtering off with suction and vacuum-drying at 40° C.The dyestuff has the formula ##STR597## and dyes cotton by the dyeingtechniques customary for reactive dyestuffs in navy hues and very highyields.

Further similar reactive dyestuffs dying cellulose fibres in navy toblack are obtained by condensing the aminodisazo components, shown inthe list below, of the general formula ##STR598## with thetrihalogenotriazines and the β-sulphatoethylsulphonylalkylanilines.

    __________________________________________________________________________    Aminodiazo component       Trihalogeno-                                                                            β-sulphatoethylsulphonyl-           No.                                                                              D.sub.1       D.sub.2   triazine  alkylaniline          Hue                __________________________________________________________________________    227                                                                               ##STR599##                                                                                  ##STR600##                                                                              ##STR601##                                                                              ##STR602##           navy               228                                                                               ##STR603##                                                                                  ##STR604##                                                                              ##STR605##                                                                              ##STR606##           navy               229                                                                               ##STR607##                                                                                  ##STR608##                                                                              ##STR609##                                                                              ##STR610##           navy               230                                                                               ##STR611##                                                                                  ##STR612##                                                                              ##STR613##                                                                              ##STR614##           navy               231                                                                               ##STR615##                                                                                  ##STR616##                                                                              ##STR617##                                                                              ##STR618##           green- ish                                                                    black              232                                                                               ##STR619##                                                                                  ##STR620##                                                                              ##STR621##                                                                              ##STR622##           navy               233                                                                               ##STR623##                                                                                  ##STR624##                                                                              ##STR625##                                                                              ##STR626##           navy               234                                                                               ##STR627##                                                                                  ##STR628##                                                                              ##STR629##                                                                              ##STR630##           navy               235                                                                               ##STR631##                                                                                  ##STR632##                                                                              ##STR633##                                                                              ##STR634##           black              236                                                                               ##STR635##                                                                                  ##STR636##                                                                              ##STR637##                                                                              ##STR638##           navy               237                                                                               ##STR639##                                                                                  ##STR640##                                                                              ##STR641##                                                                              ##STR642##           black              __________________________________________________________________________

EXAMPLE 238

50 mmol of the known copper complex compound of the formula ##STR643##are dissolved in 600 ml of water at a pH of 6.5. The solution is cooledto 0°-3°, and 7.4 g of cyanuric fluoride are added dropwise over a fewminutes. During the dropwise addition, the pH is maintained at 4.5-5.0with 2N sodium carbonate solution. Stirring is continued for about aquarter of an hour, and a neutralised solution of 17.0 g of the compoundof the formula ##STR644## in 80 ml of water is added to the primarycondensation product, and the pH of the reaction mixture is maintainedat 5.0-6.0 with sodium carbonate solution. When consumption of sodiumcarbonate has gradually come to a standstill, the temperature is allowedto rise to 20°. After the reaction is complete, the dyestuff of theformula ##STR645## is salted out, isolated and, after buffering to a pHof 6, dried in vaco at 45°.

The product dyes cellulose fibres by the dyeing techniques customary forreactive dyestuffs in navy hues and very high fixation yields.

EXAMPLE 239

A neutralised solution of 24.7 g of the component of the formula##STR646## and 2.4 g of sodium fluoride in 100 ml of water is condensedanalogously to Example 99 with 8.6 g of cyanuric fluoride.

The solution obtained is run in at 0°-2° C. to a neutral solution of 50mmol of the known copper complex compound of the formula ##STR647## andthe pH of the reaction mixture is maintained at 5-6 with 2N sodiumcarbonate solution. When absorption of sodium carbonate subsides after afew hours, the temperature is slowly raised to 20°.

After condensation is complete, the dyestuff of the formula ##STR648##is salted out, isolated and dried at 45° C. in vacuo. It dyes cellulosefibres by the dyeing techniques customary for reactive dyestuffs in bluehues.

Further reactive dyestuffs which dye cotton by the customary dyeingtechniques in very high yield are obtained by condensing the knowncopper complex compounds shown in the list below by the proceduresdescribed in Examples 238 or 239 with the trihalogenotriazines and theβ-sulphatoethylsulphonylalkylanilines.

        Trihalogeno- β     sulphatoethylsulphonyl-  No. Copper complex compound triazine alkylanilin     e Hue            240      ##STR649##      ##STR650##      ##STR651##      navy      241     ##STR652##      ##STR653##      ##STR654##      navy      242     ##STR655##      ##STR656##      ##STR657##      reddish navy      243     ##STR658##      ##STR659##      ##STR660##      navy      244     ##STR661##      ##STR662##      ##STR663##      navy      245     ##STR664##      ##STR665##      ##STR666##      dark blue      246     ##STR667##      ##STR668##      ##STR669##      green      247     ##STR670##      ##STR671##      ##STR672##      red-violet      248     ##STR673##      ##STR674##      ##STR675##      navy      249     ##STR676##      ##STR677##      ##STR678##      blue-violet

EXAMPLE 250

50 mmol of the 1:2 chromium complex of the formula ##STR679## which canbe obtained by coupling of diazotised 5-nitro-2-aminophenol with1-amino-8-hydroxynaphthalene-3,6-disulphonic acid, followed byconversion into the 1:2 chromium complex, are dissolved in 750 parts ofwater at a pH of 7. To this solution is added a solution prepared by theprocedure of Example 108 from 44.7 g of the component from Example 80and 15.5 g of cyanuric fluoride and containing the compound ##STR680##

The pH is maintained at 6-6.5 and the temperature at 20°-25°. Aftercondensation is complete, the reactive dyestuff formed is salted out,filtered off with suction and, after buffering to a pH of 6.5, gentlydried in vacuo.

The dark powder obtained is used to dye cotton in greenish grey hues.

If a 1:1 mixture of the chromium complex and the corresponding cobaltcomplex is used instead of the abovementioned pure chromium complex, adyestuff mixture is isolated which dyes cotton in neutral grey or blackhues having good lightfastness properties.

EXAMPLE 251

50 mmol of the cobalt complex of the formula ##STR681## are dissolved in800 parts by volume of water at a pH of 6, and the solution is cooled to0°-5°. 14.9 g of cyanuric fluoride are added dropwise with vigorousstirring, and the pH is maintained at 4.5-5.0 with 2N sodium carbonatesolution. After primary condensation is complete, a neutral solution isadded which contains 21.4 g of the component ##STR682## and 17.0 g ofthe component of the formula ##STR683## in 150 mol of water. The pH ismaintained at 5.5-6.0, and the temperature is allowed to rise to 20°after 2 hours. When condensation is complete, the reactive dyestuffobtained is salted out, filtered off with suction and dried in vacuo at45°. The powder obtained dyes cotton by the techniques customary forreactive dyestuffs in brown hues having good lightfastness propertiesand in high yield.

EXAMPLE 252

50 mmol of the triphendioxazine compound of the formula ##STR684## aredissolved in 900 ml of water at a pH of 6. 14.9 g of cyanuric fluorideare added dropwise to the solution at 0°-3°, and the pH is maintained at4.5-5.0 with 2N sodium carbonate solution.

After stirring is continued for a short period, a neutral solution of42.8 g of the component from Example 80 in 160 ml of water is added tothe primary condensation product, and the pH is maintained at 6.0. Afterthe condensation has gone to completion by gradually increasing thetemperature to 20°, the dyestuff of the formula ##STR685## is saltedout, isolated and dried.

It dyes cellulose fibres in greenish blue hues.

EXAMPLE 253

21.9 g of 1-(4-benzoylamino)-8-hydroxynaphthalene-3,6-disulphonic acidare dissolved in 250 ml of water at a pH of 5.5 After cooling of thesolution to 0°-3°, 7.1 g of cyanuric fluoride are swiftly addeddropwise, and the pH of the reaction mixture is maintained at 4.5 withdilute sodium carbonate solution. After stirring is continued for ashort period, a neutral solution of 16.3 g, cooled to 0°, of thecomponent from Example 81C in 80 ml of water is added, and the pH ismaintained at 5.5-6.0 overnight. After condensation is complete, adiazonium salt suspension is added which was obtained in the usualmanner by diazotisation of 8.7 g of 2-aminobenzenesulphonic acid, andthe coupling reaction is completed at a pH of 6.5-7 by addition ofsodium carbonate and initially at 0° for several hours, later increasingto 20°. The dyestuff obtained of the formula ##STR686## is isolated anddried. It produces, from a long liquor, strong red dyeings on cottonwhich have good light and wet fastness.

EXAMPLE 254

25.7 g of the triazole of the formula ##STR687## prepared by theprocedure given in European Patent 0,013,879, are dissolved in 700 ml ofwater at a pH of 6.5. The solution is cooled to 0°, and 6.9 g ofcyanuric fluoride are slowly added dropwise. The pH is maintained at6.0-6.5 with sodium bicarbonate solution. When the reaction is completeafter a few minutes, a neutral, cooled solution of 20.2 g of thecomponent from Example 80 in 80 ml of water is added, and the pH isfurther maintained at 6.5 with sodium carbonate solution.

After 2 hours, the temperature is allowed to rise to 20°. 3.7 g ofsodium nitrite are added, and the mixture is run into 20 ml of 28%strength hydrochloric acid. After one hour of after-reaction, any excessnitrous acid present is destroyed with sulphamic acid. 6.5 g ofbarbituric acid are then sprinkled in, and the coupling reaction iscarried out first at a pH of 5 by addition of sodium acetate and laterat a pH of 5.5-6 using sodium carbonate. After coupling is complete, thedyestuff is isolated and dried at 40° in vacuo. It has the formula##STR688## and dyes cotton in brilliant yellow shades.

Similar yellow dyestuffs are obtained by using the following couplingcomponents instead of barbituric acid:

2,6-Dihydroxypyridine-4-carboxylic acid

1-(4-Sulphophenyl)-3-methyl-5-pyrazolone

1-(4-Sulphophenyl)-5-pyrazolone-3-carboxylic acid

1,4-Dimethyl-2-hydroxy-6-pyridone-5-carboxamide

1,4-Dimethyl-2-hydroxy-3-sulphomethylene-6-pyridone-5-carboxamide

N-(2'-Methoxy-5'-methyl-4'-sulphophenyl)acetoacetamide

N-(2',5'-Dimethoxy-4'-sulphophenyl)acetoacetamide

1-Phenyl-3-methyl-5-aminopyrazole

1-(6,8-Disulpho-2-naphthyl)-3-methyl-5-pyrazolone

1,4-Dimethyl-2-hydroxy-5-cyano-6-pyridone.

Further yellow dyestuffs are obtained by using the sulphatoethylsulphone component from Example 81C instead of that from Example 80.

EXAMPLE 255

3.0 g of pyridine-3-carboxylic acid are added after the couplingreaction to a dyestuff solution synthesised according to Example 76. Thesolution is heated to 75° to 80° C. and the pH is maintained at 7.0using 2N sodium carbonate solution until the exchange of the fluorineatom for the nicotinic acid radical is complete. After cooling, thedyestuff can be salted out or the solution, after desalting andconcentrating, can be used as a liquid dyestuff.

The dyestuff has the formula ##STR689## and dyes cotton from a longliquor similar to the dyestuff from Example 76.

Similarly, the other fluorotriazine dyestuffs described in the previousexamples can also be converted into the 3-carboxypyridiniumtriazinedyestuff.

We claim:
 1. A reactive dyestuff of the formula: ##STR690## in which Brepresents a direct bond or a bridging member on a ring C atom of anaromatic-carbocyclic ring or on a ring C atom or N atom of anaromatic-heterocyclic ring in D;R_(a) and R_(b) are identical ordifferent and represent H, C₁₋₄ -alkyl or C₁₋₄ -alkyl substituted by OH,CN, COOH, OSO₃ H or SO₃ H; Y represents CH═CH₂ or CH₂ --CH₂ --X; Vrepresents H, halogen, C₁₋₄ -alkoxy, C₁₋₃ -alkyl, CN, COOH, CONH₂ or SO₃H; D represents the radical of a dyestuff from the formazan,phthalocyanine, anthraquinone or triphendioxazine series; U representsCl or F; W represents C₁₋₄ -alkylene; and X represents OSO₃ H, Cl, Br orF.
 2. A reactive dyestuff according to claim 1, wherein:R_(a) representsH or C₁₋₂ -alkyl; R_(b) represents H, C₁₋₃ -alkyl, β-hydroxyethyl,β-sulphatoethyl, β-carboxyethyl, β-cyanoethyl or carboxymethyl; Wrepresents CH₂, C₂ H₄, --CH₂ --CH(CH₃)-- or --(CH₂)₃ --; Y representsCH═CH₂ or CH₂ --CH₂ --X; X represents OSO₃ H or Cl; and V represents H,C₁₋₂ -alkoxy, C₁₋₂ -alkyl, COOH or SO₃ H.
 3. A reactive dyestuffaccording to claim 1, which has one of the following formulas:##STR691## in which R₈ represents H or C₁₋₂ -alkyl;Pc represents aphthalocyanine ring; Me represents a divalent metal ion; n represents 0or 1; u+v+w is 3-4, with the proviso thatw is 0.8-2.0, v is 0-1.0, and uis 1.0-3.0, A₁ represents an aliphatic, araliphatic or aromatic bridgingmember; G represents O or N-R₁₁ ; R₁₁ represents H, C₁₋₂ -alkyl, and, ifA₁ is C₂ -alkylene, R₁₁ together with R_(a) can join to form a ring; T₁and T₂ represent H, chlorine, bromine, C₁₋₄ -alkyl, C₁₋₄ -alkoxy oracylamino; R₁ -R₆ independently represent H, C₁₋₄ -alkyl, C₁₋₄ -alkoxy,hydroxyl, halogen, carboxyl, sulphonamido, alkyl- or arylcarbonylaminoor- sulphonylamino, β-sulphatoethylsulphonyl or SO₃ H, carboxymethyl orcarboxyethyl; R₇ -R₁₀ independently represent H, C₁₋₂ -alkyl, which isunsubstituted or substituted by hydroxyl, carboxyl or sulphonyl, and R₉and R₁₀ can also be joined to form a ring if A is C2-alkylene; Zrepresents a radical of the formula: ##STR692## U represents Cl or F; Arepresents a radical of the formula: ##STR693## W represents CH₂, C₂ H₄,--CH₂ --CH(CH₃)-- or --(CH₂)₃ --; Y represents CH═CH₂ or CH₂ --CH₂ --X;V represents H, C₁₋₂ -alkoxy, C₁₋₂ -alkyl, COOH or SO₃ H; and R_(b)represents H, CH₃, C₂ H₅, i--C₃ H₇, n--C₃ H₇, C₂ H₄ OH, carboxymethyl orcarboxyethyl.
 4. A reactive dyestuff according to claim 1, which has theformula: ##STR694## in which A represents ##STR695## in which Wrepresents CH₂, C₂ H₄, --CH₂ --CH(CH₃)-- or --(CH₂)₃ --;V represents H,C₁₋₂ -alkoxy, C₁₋₂ -alkyl, COOH or SO₃ H; and R_(b) represents H, CH₃,C₂ H₅, i--C₃ H₇, n--C₃ H₇, C₂ H₄ OH, carboxymethyl or carboxyethyl. 5.An azo-dyestuff selected from the group of compounds having one of theformulas 18-21 and 24-28: ##STR696## wherein R₁₆ represents alkyl,alkoxy or halogen;R₁₇ represents H, alkyl, aralkyl or aryl; R₁₈represents alkyl, aryl, aralkyl or hetaryl; and R₁₉ represents H, CN,CH₂ --SO₃ H, SO₃ H or CONH₂ ; ##STR697## wherein R₁₆ represents alkyl,alkoxy or halogen; R₂₀ represents alkyl, alkoxy, acylamino or amino; ando, p indicates ortho or para position bonding relative to the azo group;##STR698## wherein R₁₆ represents alkyl, alkoxy or halogen; ##STR699##wherein R₁₆ represents alkyl, alkoxy or halogen; and K represents theradical of a coupling component; ##STR700## wherein R₂₃ represents alkylor halogen; R₁₆ represents alkyl or alkoxy; and K represents the radicalof a coupling component; ##STR701## wherein K represents the radical ofa coupling component; ##STR702## wherein R₁₆ represents alkyl, alkoxy orarylamino; and ##STR703## wherein R₁₆ represents alkyl or alkoxy; R₂₄represents H, NH₂ or arylamino; R_(a) represents H or C₁₋₂ -alkyl; Brepresents a direct bond or a bridging member on a ring C atom of anaromatic-carbocyclic ring or on a ring C atom or N atom of anaromatic-heterocyclic ring in D; Z represents a radical of the formula:##STR704## in which A represents ##STR705## in which W represents C₂ H₄,--CH₂ --CH(CH₃)-- or --(CH₂)₃ --; Y represents CH═CH₂ or CH₂ --CH₂ --X;X represents OSO₃ H or Cl; V represents H, C₁₋₂ -alkoxy, C₁₋₂ -alkyl,COOH or SO₃ H; and R_(b) represents H, CH₃, C₂ H₅, i--C₃ H₇, n--C₃ H₇,C₂ H₄ OH, carboxymethyl or carboxyethyl.
 6. A reactive dyestuffaccording to claim 5, wherein in formulas 24-26, K is the radical of acoupling component selected from the group consisting of couplingcomponents from the pyridone, pyrazolone, aceto acid arylide andnaphthosulphonic acid series.
 7. A process for the dyeing of celluloseand/or polyamide-containing materials comprising applying to saidmaterials a reactive dyestuff according to claim
 1. 8. The processaccording to claim 7, wherein said reactive dyestuff is applied to saidmaterials in admixture with other dyestuffs for trichromatic dyeing. 9.A process for the dyeing of cellulose and/or polyamide-containingmaterials comprising applying to said materials a reactive dyestuffaccording to claim
 5. 10. The process according to claim 9, wherein saidreactive dyestuff is applied to said materials in admixture with otherdyestuffs for trichromatic dyeing.